Processes of polymerizing olefins

ABSTRACT

Disclosed herein are processes for polymerizing ethylene, acyclic olefins, and/or selected cyclic olefins, and optionally selected olefinic esters or carboxylic acids, and other monomers. The polymerizations are catalyzed by selected transition metal compounds, and sometimes other co-catalysts. Since some of the polymerizations exhibit some characteristics of living polymerizations, block copolymers can be readily made. Many of the polymers produced are often novel, particularly in regard to their microstructure, which gives some of them unusual properties. Numerous novel catalysts are disclosed, as well as some novel processes for making them. The polymers made are useful as elastomers, molding resins, in adhesives, etc. Also described herein is the synthesis of linear α-olefins by the oligomerization of ethylene using as a catalyst system a combination a nickel compound having a selected α-diimine ligand and a selected Lewis or Bronsted acid, or by contacting selected α-diimine nickel complexes with ethylene.

This application is a division of pending application Ser. No.08/590,650, filed Jan. 24, 1996, titled "α-Olefins and Olefin Polymersand Processes Therefor" which is a continuation-in-part of pending priorapplication Ser. No. 60/002,654, filed Aug. 22, 1995, is also acontinuation-in-part of pending application Ser. No. 60/007,375, filedNov. 15, 1995, is also a continuation-in-part of pending applicationSer. No. 08/473,590, filed Jun. 7, 1995, which is a continuation-in-partof prior pending application Ser. No. 08/415,283, filed Apr. 3, 1995,which is a continuation-in-part of pending prior application Ser. No.08/378,044 filed Jan. 24, 1995.

FIELD OF THE INVENTION

The invention concerns novel homo- and copolymers of ethylene and/or oneor more acyclic olefins, and/or selected cyclic olefins, and optionallyselected ester, carboxylic acid, or other functional group containingolefins as comonomers; selected transition metal containingpolymerization catalysts; and processes for making such polymers,intermediates for such catalysts, and new processes for making suchcatalysts. Also disclosed herein is a process for the production oflinear alpha-olefins by contacting ethylene with a nickel compound ofthe formula DAB!NiX₂ wherein DAB is a selected α-diimine and X ischlorine, bromine, iodine or alkyl, and a selected Lewis or Bronstedacid, or by contacting ethylene with other selected α-diimine nickelcomplexes

BACKGROUND OF THE INVENTION

Homo- and copolymers of ethylene (E) and/or one or more acyclic olefins,and/or cyclic olefins, and/or substituted olefins, and optionallyselected olefinic esters or carboxylic acids, and other types ofmonomers, are useful materials, being used as plastics for packagingmaterials, molded items, films, etc., and as elastomers for moldedgoods, belts of various types, in tires, adhesives, and for other uses.It is well known in the art that the structure of these variouspolymers, and hence their properties and uses, are highly dependent onthe catalyst and specific conditions used during their synthesis. Inaddition to these factors, processes in which these types of polymerscan be made at reduced cost are also important. Therefore, improvedprocesses for making such (new) polymers are of interest. Also disclosedherein are uses for the novel polymers.

α-Olefins are commercial materials being particularly useful as monomersand as chemical intermediates. For a review of α-olefins, includingtheir uses and preparation, see B. Elvers, et al., Ed., Ullmann'sEncyclopedia of Industrial Chemistry, 5th Ed., Vol. A13, VCHVerlagsgesellschaft mbH, Weinheim, 1989, p. 238-251. They are useful aschemical intermediates and they are often made by the oligomerization ofethylene using various types of catalysts. Therefore catalysts which arecapable or forming α-olefins from ethylene are constantly sought.

SUMMARY OF THE INVENTION

This invention concerns a polyolefin, which contains about 80 to about150 branches per 1000 methylene groups, and which contains for every 100branches that are methyl, about 30 to about 90 ethyl branches, about 4to about 20 propyl branches, about 15 to about 50 butyl branches, about3 to about 15 amyl branches, and about 30 to about 140 hexyl or longerbranches.

This invention also concerns a polyolefin which contains about 20 toabout 150 branches per 1000 methylene groups, and which contains forevery 100 branches that are methyl, about 4 to about 20 ethyl branches,about 1 to about 12 propyl branches, about 1 to about 12 butyl branches,about 1 to about 10 amyl branches, and 0 to about 20 hexyl or longerbranches.

Disclosed herein is a polymer, consisting essentially of repeat unitsderived from the monomers, ethylene and a compound of the formula CH₂═CH(CH₂)_(m) CO₂ R ¹, wherein R¹ is hydrogen, hydrocarbyl or substitutedhydrocarbyl, and m is 0 or an integer from 1 to 16, and which containsabout 0.01 to about 40 mole percent of repeat units derived from saidcompound, and provided that said repeat units derived from said compoundare in branches of the formula --CH(CH₂)_(n) CO₂ R¹, in about 30 toabout 70 mole percent of said branches n is 5 or more, in about 0 toabout 20 mole percent n is 4, in about 3 to 60 mole percent n is 1, 2and 3, and in about 1 to about 60 mole percent n is 0.

This invention concerns a polymer of one or more alpha-olefins of theformula CH₂ ═CH(CH₂)_(a) H wherein a is an integer of 2 or more, whichcontains the structure (XXV) ##STR1## wherein R³⁵ is an alkyl group andR³⁶ is an alkyl group containing two or more carbon atoms, and providedthat R³⁵ is methyl in about 2 mole percent or more of the total amountof (XXV) in said polymer.

This invention also includes a polymer of one or more alpha-olefins ofthe formula CH₂ ═CH(CH₂)_(a) H wherein a is an integer of 2 or more,wherein said polymer contains methyl branches and said methyl branchescomprise about 25 to about 75 mole percent of the total branches.

This invention also concerns a polyethylene containing the structure(XXVII) in an amount greater than can be accounted for by end groups,and preferably at least 0.5 or more of such branches per 1000 methylenegroups than can be accounted for by end groups. ##STR2##

This invention also concerns a polypropylene containing one or both ofthe structures (XXVIII) and (XXIX) and in the case of (XXIX) in amountsgreater than can be accounted for by end groups. Preferably at least 0.5more of (XXIX) branches per 1000 methylene groups than can be accountedfor by end groups, and/or at least 0.5 more of (XXVIII) per 1000methylene groups are present in the polypropylene. ##STR3##

Also described herein is an ethylene homopolymer with a density of 0.86g/ml or less.

Described herein is a process for the polymerization of olefins,comprising, contacting a transition metal complex of a bidentate ligandselected from the group consisting of ##STR4## with an olefin wherein:said olefin is selected from the group consisting of ethylene, an olefinof the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene,norbornene, or substituted norbornene;

said transition metal is selected from the group consisting of Ti, Zr,Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd;

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene substitutedhydrocarbylene to form a carbocyclic ring;

R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ is hydrogen,hydrocarbyl or substituted hydrocarbyl or R⁴⁴ and R²⁸ taken togetherform a ring;

R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ is hydrogen,substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ taken togetherform a ring;

each R³⁰ is independently hydrogen, substituted hydrocarbyl orhydrocarbyl, or two of R³⁰ taken together form a ring;

R²⁰ and R²³ are independently hydrocarbyl or substituted hydrocarbyl;

R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

n is 2 or 3;

R¹ is hydrogen, hydrocarbyl or substituted hydrocarbyl;

and provided that:

said transition metal also has bonded to it a ligand that may bedisplace by said olefin or add to said olefin;

when M is Pd, said bidentate ligand is (VIII), (XXXII) or (XXIII);

when M is Pd a diene is not present; and

when norbornene or substituted norbornene is used no other olefin ispresent.

Described herein is a process for the copolymerization of an olefin anda fluorinated olefin, comprising, contacting a transition metal complexof a bidentate ligand selected from the group consisting of ##STR5##with an olefin, and a fluorinated olefin wherein: said olefin isselected from the group consisting of ethylene and an olefin of theformula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷ ;

said transition metal is selected from the group consisting of Ni andPd;

said fluorinated olefin is of the formula H₂ C═CH(CH₂)_(a) R_(f) R⁴² ;

a is an integer of 2 to 20; R_(f) is perfluoroalkylene optionallycontaining one or more ether groups;

R⁴² is fluorine or a functional group;

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene substitutedhydrocarbylene to form a carbocyclic ring;

each R¹⁷ is independently saturated hydrocarbyl;

and provided that said transition metal also has bonded to it a ligandthat may be displaced by said olefin or add to said olefin.

This invention also concerns a copolymer of an olefin of the formula R¹⁷CH═CHR¹⁷ and a fluorinated olefin of the formula H₂ C═CH(CH₂)_(a) R_(f)R⁴², wherein:

each R¹⁷ is independently hydrogen or saturated hydrocarbyl;

a is an integer of 2 to 20; R_(f) is perfluoroalkylene optionallycontaining one or more ether groups; and

R⁴² is fluorine or a functional group;

provided that when both of R¹⁷ are hydrogen and R⁴² is fluorine, R_(f)is --(CF₂)_(b) -- wherein b is 2 to 20 or perfluoroalkylene containingat least one ether group.

Described herein is a process for the polymerization of olefins,comprising, contacting, at a temperature of about -100° C. to about+200° C.:

a first compound W, which is a neutral Lewis acid capable of abstractingeither Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anion formed is aweakly coordinating anion; or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion;

a second compound of the formula ##STR6## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, or norbornene;

wherein:

M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd the moxidation state;

y+z=m

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

Q is alkyl, hydride, chloride, iodide, or bromide;

S is alkyl, hydride, chloride, iodide, or bromide; and

provided that:

when norbornene or substituted norbornene is present, no other monomeris present;

when M is Pd a diene is not present; and

except when M is Pd, when both Q and S are each independently chloride,bromide or iodide W is capable of transferring a hydride or alkyl groupto M.

This invention includes a process for the production of polyolefins,comprising contacting, at a temperature of about -100° C. to about +200°C., one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, and norbornene; with a compound ofthe formula ##STR7## wherein: R² and R⁵ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound to the imino nitrogen atom has at least two carbon atoms bound toit;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ C(═O)-- or R¹⁵ OC (═O)--;

n is 2 or 3;

Z is a neutral Lewis base wherein the donating atom, is nitrogen, sulfuror oxygen, provided that if the donating atom is nitrogen then the pKaof the conjugate acid of that compound is less than about 6;

X is a weakly coordinating anion;

R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

M is Ni(II) or Pd(II);

each R¹⁶ is independently hydrogen or alkyl containing 1 to 10 carbonatoms;

n is 1, 2, or 3;

R⁸ is hydrocarbyl; and

T² is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,hydrocarbyl substituted with keto or ester groups but not containingolefinic or acetylenic bonds, R²³ C(═O)-- or R¹⁵ OC(═O)--;

and provided that:

when M is Pd a diene is not present; and

when norbornene or substituted norbornene is used no other monomer ispresent.

This invention includes a process for the production of polyolefins,comprising contacting, at a temperature of about -100° C. to about +200°C., one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, and norbornene; with a compound ofthe formula ##STR8## wherein: R⁴⁴ is hydrocarbyl or substitutedhydrocarbyl, and R²⁸ is hydrogen, hydrocarbyl or substituted hydrocarbylor R⁴⁴ and R²⁸ taken together form a ring;

R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ is hydrogen,substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ taken togetherform a ring;

each R³⁰ is independently hydrogen, substituted hydrocarbyl orhydrocarbyl, or two of R³⁰ taken together form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

R²⁰ and R²³ are independently hydrocarbyl or substituted hydrocarbyl;

R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl;

T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfuror oxygen, provided that if the donating atom is nitrogen then the pKaof the conjugate acid of that compound is less than about 6; and

X is a weakly coordinating anion; and

provided that:

when M is Pd or (XVIII) is used a diene is not present; and

in (XVII) M is not Pd.

This invention includes a process for the production of polyolefins,comprising contacting, at a temperature of about -100° C. to about +200°C., one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, 4-vinylcyclohexene,cyclobutene, cyclopentene, substituted norbornene, and norbornene; witha compound of the formula ##STR9## wherein: R²⁰ and R²³ areindependently hydrocarbyl or substituted hydrocarbyl;

R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl;

T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ C (═O)-- or R¹⁵ OC(═O)--;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfuror oxygen, provided that if the donating atom is nitrogen then the pKaof the conjugate acid of that compound is less than about 6;

X is a weakly coordinating anion;

R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

M is Ni(II) or Pd(II);

T² is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,hydrocarbyl substituted with keto or ester groups but not containingolefinic or acetylenic bonds, R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;

and provided that:

when M is Pd a diene is not present; and

when norbornene or substituted norbornene is used no other monomer ispresent.

Described herein is a process for the production for polyolefins,comprising contacting, at a temperature of about -100° C. to about +200°C.,

a first compound W, which is a neutral Lewis acid capable of abstractingeither Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anion formed is aweakly coordinating anion; or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion;

a second compound of the formula ##STR10## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, or norbornene;

wherein:

M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, or Ni, of oxidationstate m;

R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ is hydrogen,substituted hydrocarbyl or hydrocarbyl, or R⁴⁴ and R²⁸ taken togetherform a ring;

R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ is hydrogen,substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ taken togetherform a ring;

each R³⁰ is independently hydrogen, substituted hydrocarbyl orhydrocarbyl, or two of R³⁰ taken together form a ring;

n is 2 or 3;

y and z are positive integers;

y+z=m;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

Q is alkyl, hydride, chloride, iodide, or bromide;

S is alkyl, hydride, chloride, iodide, or bromide; and

provided that;

when norbornene or substituted norbornene is present, no other monomeris present.

Disclosed herein is a process for the production of polyolefins,comprising, contacting, at a temperature of about -100° C. to about+200° C., one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, and norbornene;optionally a source of X; with a compound of the formula ##STR11##wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene substitutedhydrocarbylene to form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that R¹⁷ contains no olefinic bonds;

T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;

R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

E is halogen or --OR¹⁸ ;

R¹⁸ is hydrocarbyl not containing olefinic or acetylenic bonds; and

X is a weakly coordinating anion;

provided that, when norbornene or substituted norbornene is present, noother monomer is present.

Described herein is a process for the polymerization of olefins,comprising, contacting, at a temperature of about -100° C. to about+200° C.:

a first compound W, which is a neutral Lewis acid capable of abstractingeither Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anion formed is aweakly coordinating anion; or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion;

a second compound of the formula ##STR12## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, 4-vinylcyclohexene, cyclobutene,cyclopentene, substituted norbornene, or norbornene;

wherein:

M is Ni(II), Co(II), Fe(II), or Pd(II);

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

Q is alkyl, hydride, chloride, iodide, or bromide;

S is alkyl, hydride, chloride, iodide, or bromide; and

provided that;

when norbornene or substituted norbornene is present, no other monomeris present;

when M is Pd a diene is not present; and

except when M is Pd, when both Q and S are each independently chloride,bromide or iodide W is capable of transferring a hydride or alkyl groupto M.

Included herein is a polymerization process, comprising, contacting acompound of the formula Pd(R¹³ CN)₄ !X₂ or a combination of Pd OC(O)R⁴⁰!₂ and HX; a compound of the formula ##STR13## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclopentene, cyclobutene, substitutednorbornene, and norbornene; wherein:

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that R¹⁷ contains no olefinic bonds;

R¹³ is hydrocarbyl;

R⁴⁰ is hydrocarbyl or substituted hydrocarbyl and

X is a weakly coordinating anion;

provided that, when norbornene or substituted norbornene is present, noother monomer is present.

Also described herein is a polymerization process, comprising;

contacting Ni 0!, Pd 0! or Ni I! compound containing a ligand which maybe displaced by a ligand of the formula (VIII), (XXX), (XXXII) or(XXIII);

a second compound of the formula ##STR14## an oxidizing agent; a sourceof a relatively weakly coordinating anion;

and one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ C═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene;

wherein:

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

R¹³ is hydrocarbyl;

R⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R²⁸ is hydrogen,hydrocarbyl or substituted hydrocarbyl or R⁴⁴ and R²⁸ taken togetherform a ring;

R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ is hydrogen,substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ taken togetherform a ring;

each R³⁰ is independently hydrogen, substituted hydrocarbyl orhydrocarbyl, or two of R³⁰ taken together form a ring; R³¹ isindependently hydrogen, hydrocarbyl or substituted hydrocarbyl;

R⁴⁶ and R⁴⁷ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

R⁴⁸ and R⁴⁹ are each independently hydrogen, hydrocarbyl, or substitutedhydrocarbyl;

R²⁰ and R²³ are independently hydrocarbyl or substituted hydrocarbyl;

n is 2 or 3;

R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl; and

X is a weakly coordinating anion;

provided that;

when norbornene or substituted norbornene is present, no other monomeris present;

when said Pd 0! compound is used, a diene is not present; and

when said second compound is (XXX) only an Ni 0! or Ni I! compound isused.

Described herein is a polymerization process, comprising, contacting anNi 0! complex containing a ligand or ligands which may be displaced by(VIII), oxygen, an alkyl aluminum compound, and a compound of theformula ##STR15## and one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene, substituted norbornene, andnorbornene; wherein:

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; and

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

provided that, when norbornene or substituted norbornene is present, noother monomer is present.

A polymerization process, comprising, contacting oxygen and an alkylaluminum compound, or a compound of the formula HX, and a compound ofthe formula ##STR16## and one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene, substituted norbornene, andnorbornene; wherein:

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; and

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

X is a weakly coordinating anion; and

provided that, when norbornene or substituted norbornene is present, noother monomer is present.

Described herein is a polymerization process, comprising, contacting anNi 0! complex containing a ligand or ligands which may be displaced by(VIII), HX or a Bronsted acidic solid, and a compound of the formula##STR17## and one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene, and norbornene;wherein:

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; and

X is a weakly coordinating anion;

provided that, when norbornene or substituted norbornene is present, noother monomer is present

Described herein is a process for the polymerization of olefins,comprising, contacting, at a temperature of about -100° C. to about+200° C.:

a first compound W, which is a neutral Lewis acid capable of abstractingeither Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anion formed is aweakly coordinating anion; or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion;

a second compound of the formula ##STR18## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, or norbornene;

wherein:

M is Ni(II) or Pd(II);

R²⁰ and R²³ are independently hydrocarbyl or substituted hydrocarbyl;

R²¹ and R²² are each in independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

Q is alkyl, hydride, chloride, iodide, or bromide;

S is alkyl, hydride, chloride, iodide, or bromide; and

provided that;

when norbornene or substituted norbornene is present, no other monomeris present;

when M is Pd a diene is not present; and

except when M is Pd, when both Q and S are each independently chloride,bromide or iodide W is capable of transferring a hydride or alkyl groupto M.

This invention also concerns a process for the polymerization ofolefins, comprising, contacting, at a temperature of about -100° C. toabout +200° C., a compound of the formula ##STR19## and one or moremonomers selected from the group consisting of ethylene, an olefin ofthe formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclopentene, cyclobutene,substituted norbornene, and norbornene; wherein:

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that R¹⁷ contains no olefinic bonds; and

each R²⁷ is independently hydrocarbyl;

each X is a weakly coordinating anion;

provided that, when norbornene or substituted norbornene is present, noother monomer is present.

This invention also concerns a process for the polymerization ofolefins, comprising, contacting, at a temperature of about -100° C. toabout +200° C.:

a first compound W, which is a neutral Lewis acid capable of abstractingeither Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that the anion formed is aweakly coordinating anion; or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion;

a second compound of the formula ##STR20## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclopentene, cyclobutene, substitutednorbornene, and norbornene; wherein:

R⁴⁶ and R⁴⁷ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

R⁴⁸ and R⁴⁹ are each independently hydrogen, hydrocarbyl, or substitutedhydrocarbyl;

each R³¹ is independently hydrocarbyl, substituted hydrocarbyl orhydrogen;

M is Ti, Zr, Co, V, Cr, a rare earth metal, Fe, Sc, Ni, or Pd ofoxidation state m;

y and z are positive integers;

y+z=m;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

Q is alkyl, hydride, chloride, iodide, or bromide;

S is alkyl, hydride, chloride, iodide, or bromide; and

provided that;

when norbornene or substituted norbornene is present, no other monomeris present;

when M is Pd a diene is not present; and

except when M is Pd, when both Q and S are each independently chloride,bromide or iodide W is capable of transferring a hydride or alkyl groupto M.

Disclosed herein is a compound of the formula ##STR21## wherein: R² andR⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfuror oxygen, provided that if the donating atom is nitrogen then the pKaof the conjugate acid of that compound is less than about 6;

X is a weakly coordinating anion; and

R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

provided that when R³ and R⁴ taken together are hydrocarbylene to form acarbocyclic ring, Z is not an organic nitrile.

Described herein is a compound of the formula ##STR22## wherein: R⁵⁰ issubstituted phenyl;

R⁵¹ is phenyl or substituted phenyl;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

and provided that groups in the 2 and 6 positions of R⁵⁰ have adifference in E_(s) of about 0.60 or more.

Described herein is a compound of the formula ##STR23## wherein: R⁵² issubstituted phenyl;

R⁵³ is phenyl or substituted phenyl;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

Q is alkyl, hydride, chloride, bromide or iodide;

S is alkyl, hydride, chloride, bromide or iodide;

and provided that;

groups in the 2 and 6 positions of R⁵² have a difference in E_(s) of0.15 or more; and

when both Q and S are each independently chloride, bromide or iodide Wis capable of transferring a hydride or alkyl group to Ni.

This invention includes a compound of the formula ##STR24## wherein: R²and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, or substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;

R¹⁵ is hydrocarbyl not containing an olefinic or acetylenic bond;

Z is a neutral Lewis acid wherein the donating atom is nitrogen, sulfuror oxygen, provided that, if the donating atom is nitrogen, then the pKaof the conjugate acid of that compound is less than about 6; and

X is a weakly coordinating anion.

This invention also concerns a compound of the formula ##STR25##wherein: R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

M is Ni(II) or Pd(II);

each R¹⁶ is independently hydrogen or alkyl containing 1 to 10 carbonatoms;

n is 1, 2, or 3;

X is a weakly coordinating anion; and

R⁸ is hydrocarbyl.

Also disclosed herein is a compound of the formula ##STR26## wherein: R²and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

E is halogen or --OR¹⁸ ;

R¹⁸ is hydrocarbyl not containing olefinic or acetylenic bonds;

T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;

R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds; and

X is a weakly coordinating anion.

Included herein is a compound of the formula (η⁴ -1,5-COD)PdT¹ Z!⁺ X⁻,wherein:

T¹ is hydrocarbyl not containing olefinic or acetylenic bonds;

X is a weakly coordinating anion;

COD is 1,5-cyclooctadiene;

Z is R¹⁰ CN; and

R¹⁰ is hydrocarbyl not containing olefinic or acetylenic bonds.

Also included herein is a compound of the formula ##STR27## wherein: Mis Ni(II) or Pd(II);

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹¹ is independently hydrogen, alkyl or --(CH₂)_(m) CO₂ R¹ ;

T³ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,or --CH₂ CH₂ CH₂ CO₂ R⁸ ;

P is a divalent group containing one or more repeat units derived fromthe polymerization of one or more of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, or norbornene and, when M is Pd(II), optionally one or moreof: a compound of the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹, CO, or a vinylketone;

R⁸ is hydrocarbyl;

m is 0 or an integer from 1 to 16;

R¹ is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1to 10 carbon atoms;

and X is a weakly coordinating anion;

provided that, when M is Ni(II), R¹¹ is not --CO₂ R⁸.

Also described herein is a compound of the formula ##STR28## wherein: R²and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

T² is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,hydrocarbyl substituted with keto or ester groups but not containingolefinic or acetylenic bonds, R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;

R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds; and

X is a weakly coordinating anion.

Included herein is a process for the production of polyolefins,comprising, contacting, at a temperature of about -100° C. to about+200° C., a compound of the formula ##STR29## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, and norbornene,

wherein:

M is Ni(II) or Pd(II);

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹¹ is independently hydrogen, alkyl or --(CH₂)_(m) CO₂ R¹ ;

T³ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,or --CH₂ CH₂ CH₂ CO₂ R⁸ ;

P is a divalent group containing one or more repeat units derived fromthe polymerization of one or monomers selected from the group consistingof ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene, and norbornene, and,when M is Pd(II), optionally one or more of: a compound of the formulaCH₂ ═CH(CH₂)_(m) CO₂ R¹, CO or a vinyl ketone;

R⁸ is hydrocarbyl;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; R¹ is hydrogen, or hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms;

m is 0 or an integer of 1 to 16;

and X is a weakly coordinating anion;

provided that:

when M is Pd a diene is not present;

when norbornene or substituted norbornene is present, no other monomeris present; and

further provided that, when M is Ni(II), R¹¹ is not --CO₂ R⁸.

Included herein is a process for the production of polyolefins,comprising, contacting, at a temperature of about -100° C. to about+200° C., a compound of the formula ##STR30## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, and norbornene,

wherein:

M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd ofoxidation state m;

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹¹ is independently hydrogen, or alkyl, or both of R¹¹ takentogether are hydrocarbylene to form a carbocyclic ring;

T³ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,or --CH₂ CH₂ CH₂ CO₂ R⁸ ;

P is a divalent group containing one or more repeat units derived fromthe polymerization of one or monomers selected from the group consistingof ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹,cyclopentene, cyclobutene, substituted norbornene, and norbornene, and,when M is Pd(II), optionally one or more of: a compound of the formulaCH₂ ═CH(CH₂)_(m) CO₂ R¹, CO, or a vinyl ketone;

R⁸ is hydrocarbyl;

a is 1 or 2;

y+a+1=m;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; R¹ is hydrogen, or hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms;

m is 0 or an integer of 1 to 16;

and X is a weakly coordinating anion;

provided that:

when norbornene or substituted norbornene is present, no other monomeris present;

when M is Pd a diene is not present; and

further provided that, when M is Ni(II), R¹¹ is not --CO₂ R⁸.

Also described herein is a compound of the formula ##STR31## wherein: Mis Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd of oxidationstate m;

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹¹ is independently hydrogen, or alkyl, or both of R¹¹ takentogether are hydrocarbylene to form a carbocyclic ring;

T³ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,or --CH₂ CH₂ CH₂ CO₂ R⁸ ;

P is a divalent group containing one or more repeat units derived fromthe polymerization of one or monomers selected from the group consistingof ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷,cyclopentene, cyclobutene, substituted norbornene, and norbornene, andoptionally, when M is Pd(II), one or more of: a compound of the formulaCH₂ ═CH(CH₂)_(m) CO₂ R¹, CO, or a vinyl ketone;

Q is a monovalent anion;

R⁸ is hydrocarbyl;

a is 1 or 2;

y+a+1=m;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

R¹ is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1to 10 carbon atoms;

m is 0 or an integer of 1 to 16; and

and X is a weakly coordinating anion;

and provided that when M is Pd a diene is not present.

Described herein is a process, comprising, contacting, at a temperatureof about -40° C. to about +60° C., a compound of the formula (η⁴-1,5-COD)PdT¹ Z!⁺ X⁻ and a diimine of the formula ##STR32## to produce acompound of the formula ##STR33## wherein: T¹ is hydrogen, hydrocarbylnot containing olefinic or acetylenic bonds, R¹⁵ C(═O)-- or R¹⁵OC(═O)--;

X is a weakly coordinating anion;

COD is 1,5-cyclooctadiene;

Z is R¹⁰ CN;

R¹⁰ is hydrocarbyl not containing olefinic or acetylenic bonds;

R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it; and

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring.

Described herein is a process, comprising, contacting, at a temperatureof about -80° C. to about +20° C., a compound of the formula (η⁴-1,5-COD)PdMe₂ and a diimine of the formula ##STR34## to produce acompound of the formula ##STR35## wherein: COD is 1,5-cyclooctadiene;

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it; and

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring.

Also disclosed herein is a compound of the formula ##STR36## wherein: R²and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R²⁷ is hydrocarbyl; and

each X is a weakly coordinating anion.

This invention includes a compound of the formula ##STR37## wherein: Mis Ni(II) or Pd(II);

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹⁴ is independently hydrogen, alkyl or --(CH₂)_(m) CO₂ R¹ ;

R¹ is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1to 10 carbon atoms;

T⁴ is alkyl, --R⁶⁰ C(O)OR⁸, R¹⁵ (C═O)-- or R¹⁵ OC(═O)--;

R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

R⁶⁰ is alkylene not containing olefinic or acetylenic bonds;

R⁸ is hydrocarbyl;

and X is a weakly coordinating anion;

and provided that when R¹⁴ is --(CH₂)_(m) CO₂ R¹, or T⁴ is not alkyl, Mis Pd(II).

Described herein is a homopolypropylene with a glass transitiontemperature of -30° C. or less, and containing at least about 50branches per 1000 methylene groups.

This invention also concerns a homopolymer of cyclopentene having adegree of polymerization of about 30 or more and an end of melting pointof about 100° C. to about 320° C., provided that said homopolymer hasless than 5 mole percent of enchained linear olefin containing pentyleneunits.

In addition, disclosed herein is a homopolymer or copolymer ofcyclopentene that has an X-ray powder diffraction pattern that hasreflections at approximately 17.3°, 19.3°, 24.2°, and 40.7° 2θ.

Another novel polymer is a homopolymer of cyclopentene wherein at least90 mole percent of enchained cyclopentylene units are 1,3-cyclopentyleneunits, and said homopolymer has an average degree of polymerization of30 more.

Described herein is a homopolymer of cyclopentene wherein at least 90mole percent of enchained cyclopentylene units arecis-1,3-cyclopentylene, and said homopolymer has an average degree ofpolymerization of about 10 or more.

Also described is a copolymer of cyclopentene and ethylene wherein atleast 75 mole percent of enchained cyclopentylene units are1,3-cyclopentylene units.

This invention concerns a copolymer of cyclopentene and ethylene whereinthere are at least 20 branches per 1000 methylene carbon atoms.

Described herein is a copolymer of cyclopentene and ethylene wherein atleast 50 mole percent of the repeat units are derived from cyclopentene.

Disclosed herein is a copolymer of cyclopentene and an α-olefin.

This invention also concerns a polymerization process, comprising,contacting an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, whereineach R¹⁷ is independently hydrogen, hydrocarbyl, or substitutedhydrocarbyl provided that any olefinic bond in said olefin is separatedfrom any other olefinic bond or aromatic ring by a quaternary carbonatom or at least two saturated carbon atoms with a catalyst, whereinsaid catalyst:

contains a nickel or palladium atom in a positive oxidation state;

contains a neutral bidentate ligand coordinated to said nickel orpalladium atom, and wherein coordination to said nickel or palladiumatom is through two nitrogen atoms or a nitrogen atom and a phosphorousatom; and

said neutral bidentate ligand, has an Ethylene Exchange Rate of lessthan 20,000 L-mol⁻¹ s⁻¹ when said catalyst contains a palladium atom,and less than 50,000 L-mol⁻¹ s⁻¹ when said catalyst contains a nickelatom;

and provided that when Pd is present a diene is not present.

Described herein is a process for the polymerization of olefins,comprising, contacting, at a temperature of about -100° C. to about+200° C.:

a first compound which is a salt of an alkali metal cation and arelatively noncoordinating monoanion;

a second compound of the formula ##STR38## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═C₂ or R¹ H═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, or norbornene;

wherein:

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁵ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that R¹⁷ contains no olefinic bond;

T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;

S is chloride, iodide, or bromide; and

provided that, when norbornene or substituted norbornene is present, noother monomer is present.

Described herein is a polyolefin, comprising, a polymer made bypolymerizing one or more monomers of the formula H₂ C═CH(CH₂)_(e) G bycontacting said monomers with a transition metal containing coordinationpolymerization catalyst, wherein:

each G is independently hydrogen or --CO₂ R¹ ;

each e is independently 0 or an integer of 1 to 20;

each R is independently hydrogen, hydrocarbyl or substitutedhydrocarbyl;

and provided that:

said polymer has at least 50 branches per 1000 methylene groups;

in at least 50 mole percent of said monomers G is hydrogen; and

except when no branches should be theoretically present, the number ofbranches per 1000 methylene groups is 90% or less than the number oftheoretical branches per 1000 methylene groups, or the number ofbranches per 1000 methylene groups is 110% or more of theoreticalbranches per 1000 methylene groups, and

when there should be no branches theoretically present, said polyolefinhas 50 or more branches per 1000 methylene groups;

and provided that said polyolefin has at least two branches of differentlengths containing less than 6 carbon atoms each.

Also described herein is a polyolefin, comprising, a polymer made bypolymerizing one or more monomers of the formula H₂ C═CH(CH₂)_(e) G bycontacting said monomers with a transition metal containing coordinationpolymerization catalyst, wherein:

each G is independently hydrogen or --CO₂ R¹ ;

each e is independently 0 or an integer of 1 to 20;

R¹ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

and provided that:

said polymer has at least 50 branches per 1000 methylene groups;

in at least 50 mole percent of said monomers G is hydrogen;

said polymer has at least 50 branches of the formula --(CH₂)_(f) G per1000 methylene groups, wherein when G is the same as in a monomer ande≠f, and/or for any single monomer of the formula H₂ C═CH(CH₂)_(e) Gthere are less than 90% of the number of theoretical branches per 1000methylene groups, or more than 110% of the theoretical branches per 1000methylene groups of the formula --(CH₂)_(f) G and f=e, and wherein f is0 or an integer of 1 or more;

and provided that said polyolefin has at least two branches of differentlengths containing less than 6 carbon atoms.

This invention concerns a process for the formation of linear α-olefins,comprising, contacting, at a temperature of about -100° C. to about+200° C.:

ethylene;

a first compound W, which is a neutral Lewis acid capable of abstractingX⁻ to form WX⁻, provided that the anion formed is a weakly coordinatinganion, or a cationic Lewis or Bronsted acid whose counterion is a weaklycoordinating anion; and

a second compound of the formula ##STR39## wherein: R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; and

Q and S are each independently chlorine, bromine, iodine or alkyl; and

wherein an α-olefin containing 4 to 40 carbon atoms is produced.

This invention also concerns a process for the formation of linearα-olefins, comprising, contacting, at a temperature of about -100° C. toabout +200° C.:

ethylene and a compound of the formula ##STR40## wherein: R² and R⁵ areeach independently hydrocarbyl or substituted hydrocarbyl;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

T¹ is hydrogen or n-alkyl containing up to 38 carbon atoms;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur,or oxygen, provided that if the donating atom is nitrogen then the pKaof the conjugate acid of that compound (measured in water) is less thanabout 6;

U is n-alkyl containing up to 38 carbon atoms; and

X is a noncoordinating anion;

and wherein an α-olefin containing 4 to 40 carbon atoms is produced.

Another novel process is a process for the formation of linearα-olefins, comprising, contacting, at a temperature of about -100° C. toabout +200° C.:

ethylene;

and a Ni II! of ##STR41## R² and R⁵ are each independently hydrocarbylor substituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene substitutedhydrocarbylene to form a carbocyclic ring and

wherein an α-olefin containing 4 to 40 carbon atoms is produced.

Also described herein is a process for the production of polyolefins,comprising, contacting, at a temperature of about 0° C. to about +200°C., a compound of the formula ##STR42## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, and norbornene,

wherein:

M is Ni(II) or Pd(II);

A is a π-allyl or π-benzyl group;

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each r¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

and X is a weakly coordinating anion;

and provided that:

when M is Pd a diene is not present; and

when norbornene or substituted norbornene is present, no other monomeris present.

The invention also includes a compound of the formula ##STR43## wherein:M is Ni (II) or Pd(II)

A is a π-allyl or π-benzyl group;

R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it;

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms;

and X is a weakly coordinating anion;

and provided that when M is Pd a diene is not present.

This invention also includes a compound of the formula ##STR44##wherein: R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring;

R⁵⁴ is hydrocarbyl or substituted hydrocarbyl, provided that the carbonatom bound directly to the imino nitrogen atom has at least two carbonatoms bound to it;

each R⁵⁵ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or a functional group;

W is alkylene or substituted alkylene containing 2 or more carbon atoms;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur,or oxygen, provided that if the donating atom is nitrogen then the pKaof the conjugate acid of that compound (measured in water) is less thanabout 6, or an olefin of the formula R¹⁷ CH═CHR¹⁷ ;

each R¹⁷ is independently hydrogen, saturated hydrocarbyl or substitutedsaturated hydrocarbyl; and

X is a weakly coordinating anion;

and provided that when M is Ni, W is alkylene and each R¹⁷ isindependently hydrogen or saturated hydrocarbyl.

This invention also includes a process for the production of a compoundof the formula ##STR45## comprising, heating a compound of the formula##STR46## at a temperature of about -30° C. to about +100° for asufficient time to produce (XXXVIII), and wherein:

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

R⁵⁴ is hydrocarbyl or substituted hydrocarbyl, provided that the carbonatom bound directly to the imino nitrogen atom has at least two carbonatoms bound to it;

each R⁵⁵ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or a functional group;

R⁵⁶ is alkyl containing 2 to 30 carbon atoms;

P⁵ is alkyl,

W is alkylene containing 2 to 30 carbon atoms;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur,or oxygen, provided that if the donating atom is nitrogen then the pKaof the conjugate acid of that compound (measured in water) is less thanabout 6; and

X is a weakly coordinating anion.

This invention also concerns a process for the polymerization ofolefins, comprising, contacting a compound of the formula ##STR47## andone or more monomers selected from the group consisting of ethylene, anolefin of the formula R¹⁷ CH═CH₂, or R¹⁷ CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, and norbornene,

wherein:

R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring;

R⁵⁴ is hydrocarbyl or substituted hydrocarbyl, provided that the carbonatom bound directly to the imino nitrogen atom has at least two carbonatoms bound to it;

each R⁵⁵ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or a functional group;

w is alkylene or substituted alkylene containing 2 or more carbon atoms;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur,or oxygen, provided that if the donating atom is nitrogen then the pKaof the conjugate acid of that compound (measured in water) is less thanabout 6, or an olefin of the formula R¹⁷ CH═CHR¹⁷ ;

each R¹⁷ is independently hydrogen, saturated hydrocarbyl or substitutedsaturated hydrocarbyl; and

X is a weakly coordinating anion;

and provided that:

when M is Ni, W is alkylene and each R¹⁷ is independently hydrogen orsaturated hydrocarbyl;

and when norbornene or substituted norbornene is present, no othermonomer is present.

This invention also concerns a homopolypropylene containing about 10 toabout 700 δ+ methylene groups per 1000 total methylene groups in saidhomopolypropylene.

Described herein is a homopolypropylene wherein the ratio of δ+:γmethylene groups is about 0.5 to about 7.

Also included herein is a homopolypropylene in which about 30 to about85 mole percent of the monomer units are enchained in an ω,1 fashion.

DETAILS OF THE INVENTION

Herein certain terms are used to define certain chemical groups orcompounds. These terms are defined below.

A "hydrocarbyl group" is a univalent group containing only carbon andhydrogen. If not otherwise stated, it is preferred that hydrocarbylgroups herein contain 1 to about 30 carbon atoms.

By "not containing olefinic or acetylenic bonds" is meant the groupingdoes not contain olefinic carbon-carbon double bonds (but aromatic ringsare not excluded) and carbon-carbon triple bonds.

By "substituted hydrocarbyl" herein is meant a hydrocarbyl group whichcontains one or more substituent groups which are inert under theprocess conditions to which the compound containing these groups issubjected. The substituent groups also do not substantially interferewith the process. If not otherwise stated, it is preferred thatsubstituted hydrocarbyl groups herein contain 1 to about 30 carbonatoms. Included in the meaning of "substituted" are heteroaromaticrings.

By an alkyl aluminum compound is meant a compound in which at least onealkyl group is bound to an aluminum atom. Other groups such as alkoxide,oxygen, and halogen may also be bound to aluminum atoms in the compound.

By "hydrocarbylene" herein is meant a divalent group containing onlycarbon and hydrogen. Typical hydrocarbylene groups are --(CH₂)₄ --,--CH₂ CH(CH₂ CH₃)CH₂ CH₂ -- and ##STR48##

If not otherwise stated, it is preferred that hydrocarbylene groupsherein contain 1 to about 30 carbon atoms.

By "substituted hydrocarbylene" herein is meant a hydrocarbylene groupwhich contains one or more substituent groups which are inert under theprocess conditions to which the compound containing these groups issubjected. The substituent groups also do not substantially interferewith the process. If not otherwise stated, it is preferred thatsubstituted hydrocarbylene groups herein contain 1 to about 30 carbonatoms. Included within the meaning of "substituted" are heteroaromaticrings.

By substituted norbornene is meant a norbornene which is substitutedwith one or more groups which does not interfere substantially with thepolymerization. It is preferred that substituent groups (if they containcarbon atoms) contain 1 to 30 carbon atoms. Examples of substitutednorbornenes are ethylidene norbornene and methylene norbornene.

By "saturated hydrocarbyl" is meant a univalent group containing onlycarbon and hydrogen which contains no unsaturation, such as olefinic,acetylenic, or aromatic groups. Examples of such groups include alkyland cycloalkyl. If not otherwise stated, it is preferred that saturatedhydrocarbyl groups herein contain 1 to about 30 carbon atoms.

By "neutral Lewis base" is meant a compound, which is not an ion, whichcan act as a Lewis base. Examples of such compounds include ethers,amines, sulfides, and organic nitrites.

By "cationic Lewis acid" is meant a cation which can act as a Lewisacid. Examples of such cations are sodium and silver cations.

By "α-olefin" is meant a compound of the formula CH₂ ═CHR¹⁹, wherein R¹⁹is n-alkyl or branched alkyl, preferably n-alkyl.

By "linear α-olefin" is meant a compound of the formula CH₂ ═CHR¹⁹,wherein R¹⁹ is n-alkyl. It is preferred that the linear α-olefin have 4to 40 carbon atoms.

By a "saturated carbon atom" is meant a carbon atom which is bonded toother atoms by single bonds only. Not included in saturated carbon atomsare carbon atoms which are part of aromatic rings.

By a quaternary carbon atom is meant a saturated carbon atom which isnot bound to any hydrogen atoms. A preferred quaternary carbon atom isbound to four other carbon atoms.

By an olefinic bond is meant a carbon-carbon double bond, but does notinclude bonds in aromatic rings.

By a rare earth metal is meant one of lanthanum, cerium, praeseodymium,neodymium, promethium, samarium, europium, gadolinium, terbium,dysprosium, holmium, erbium, thulium, ytterbium or lutetium.

This invention concerns processes for making polymers, comprising,contacting one or more selected olefins or cycloolefins, and optionallyan ester or carboxylic acid of the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹, andother selected monomers, with a transition metal containing catalyst(and possibly other catalyst components). Such catalysts are, forinstance, various complexes of a diimine with these metals. By a"polymerization process herein (and the polymers made therein)" is meanta process which produces a polymer with a degree of polymerization (DP)of about 20 or more, preferably about 40 or more except where otherwisenoted, as in P in compound (VI)! By "DP" is meant the average number ofrepeat (monomer) units in the polymer.

One of these catalysts may generally be written as ##STR49## wherein: Mis Ni(II), Co(II), Fe(II) or Pd(II); R² and R⁵ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound to the imino nitrogen atom has at least two carbon atoms bound toit; R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; Q is alkyl, hydride,chloride, iodide, or bromide; and S is alkyl, hydride, chloride, iodide,or bromide. Preferably M is Ni(II) or Pd(II).

In a preferred form of (I), R³ and R⁴ are each independently hydrogen orhydrocarbyl. If Q and/or S is alkyl, it is preferred that the alkylcontains 1 to 4 carbon atoms, and more preferably is methyl.

Another useful catalyst is ##STR50## wherein: R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; T¹ ishydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R¹⁵C(═O)-- or R¹⁵ OC(═O)--; Z is a neutral Lewis base wherein the donatingatom is nitrogen, sulfur or oxygen, provided that, if the donating atomis nitrogen, then the pKa of the conjugate acid of that compound is lessthan about 6; X is a weakly coordinating anion; and R¹⁵ is hydrocarbylnot containing olefinic or acetylenic bonds.

In one preferred form of (II), R³ and R⁴ are each independently hydrogenor hydrocarbyl. In a more preferred form of (II), T¹ is alkyl, and T¹ isespecially preferably methyl. It is preferred that Z is R⁶ ₂ O or R⁷ CN,wherein each R⁶ is independently hydrocarbyl and R⁷ is hydrocarbyl. Itis preferred that R⁶ and R⁷ are alkyl, and it is more preferred thatthey are methyl or ethyl. It is preferred that X⁻ is BAF, SbF₆, PF₆ orBF₄. ##STR51## wherein: R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, or substitutedhydrocarbylene, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; T¹ is hydrogen, hydrocarbylnot containing olefinic or acetylenic bonds, R¹⁵ C(═O)-- or R¹⁵ OC(═O)--; Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound is less than about 6; Xis a weakly coordinating anion; and R¹⁵ is hydrocarbyl not containingolefinic or acetylenic bonds.

In one preferred form of (III), R³ and R⁴ are each independentlyhydrogen, hydrocarbyl. In a more preferred form of (III) T¹ is alkyl,and T¹ is especially preferably methyl. It is preferred that Z is R⁶ ₂ Oor R⁷ CN, wherein each R⁶ is independently hydrocarbyl and R⁷ ishydrocarbyl. It is preferred that R⁶ and R⁷ are alkyl, and it isespecially preferred that they are methyl or ethyl. It is preferred thatX³¹ is BAF⁻, SbF₆ ⁻, PF₆ ⁻ or BF₄ ⁻.

Relatively weakly coordinating anions are known to the artisan. Suchanions are often bulky anions, particularly those that may delocalizetheir negative charge. Suitable weakly coordinating anions in thisApplication include (Ph)₄ B³¹ (Ph=phenyl), tetrakis3,5-bis(trifluoromethyl)phenyl!borate (herein abbreviated BAF), PF₆ ⁻,BF₄ ⁻, SbF₆ ⁻, trifluoromethanesulfonate, p-toluenesulfonate, (R_(f)SO₂)₂ N⁻, and (C₆ F₅)₄ B⁻. Preferred weakly coordinating anions includeBAF⁻, PF₆ ⁻, BF₄ ⁻, and SbF₆ ⁻.

Also useful as a polymerization catalyst is a compound of the formula##STR52## wherein: R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl orR³ and R⁴ taken together are hydrocarbylene or substitutedhydrocarbylene to form a ring; M is Ni(II) or Pd(II); each R¹⁶ isindependently hydrogen or alkyl containing 1 to 10 carbon atoms; n is 1,2, or 3; X is a weakly coordinating anion; and R⁸ is hydrocarbyl.

It is preferred that n is 3, and all of R¹⁶ are hydrogen. It is alsopreferred that R⁸ is alkyl or substituted alkyl, especially preferredthat it is alkyl, and more preferred that R⁸ is methyl.

Another useful catalyst is ##STR53## wherein: R² and R⁵ are hydrocarbylor substituted hydrocarbyl, provided that the carbon atom bound directlyto the imino nitrogen atom has at least two carbon atoms bound to it; R³and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; T¹ is hydrogen, hydrocarbylnot containing olefinic or acetylenic bonds, R¹⁵ C(═O)-- or R¹⁵OC(═O)--; R¹⁵ is hydrocarbyl not containing olefinic or acetylenicbonds; E is halogen or --OR¹⁸ ; R¹⁸ is hydrocarbyl not containingolefinic or acetylenic bonds; and X is a weakly coordinating anion. Itis preferred that T¹ is alkyl containing 1 to 4 carbon atoms, and morepreferred that it is methyl. In other preferred compounds (V), R³ and R⁴are methyl or hydrogen and R² and R⁵ are 2,6-diisopropylphenyl and X isBAF. It is also preferred that E is chlorine.

Another useful catalyst is a compound of the formula ##STR54## wherein:R² and R⁵ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it; R³ and R⁴ are each independentlyhydrogen, hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ takentogether are hydrocarbylene or substituted hydrocarbylene to form aring; T² is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, hydrocarbyl substituted with keto or ester groups but notcontaining olefinic or acetylenic bonds, R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;R¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds; and X isa weakly coordinating anion. In a more preferred form of (VII), T² isalkyl containing 1 to 4 carbon atoms and T² is especially preferablymethyl. It is preferred that X is perfluoroalkylsulfonate, especiallytrifluoromethanesulfonate (triflate). If X⁻ is an extremely weaklycoordinating anion such as BAF, (VII) may not form. Thus it may be saidthat (VII) forms usually with weakly, but perhaps not extremely weakly,coordinating anions.

In all compounds, intermediates, catalysts, processes, etc. in whichthey appear it is preferred that R² and R⁵ are each independentlyhydrocarbyl, and in one form it is especially preferred that R² and R⁵are both 2,6-diisopropylphenyl, particularly when R³ and R⁴ are eachindependently hydrogen or methyl. It is also preferred that R³ and R⁴are each independently hydrogen, hydrocarbyl or taken togetherhydrocarbylene to form a carbocyclic ring.

Compounds of the formula (I) wherein M is Pd, Q is alkyl and S ishalogen may be made by the reaction of the corresponding1,5-cyclooctadiene (COD) Pd complex with the appropriate diimine. When Mis Ni, (I) can be made by the displacement of a another ligand, such asa dialkylether or a polyether such as 1,2-dimethoxyethane, by anappropriate diimine.

Catalysts of formula (II), wherein X⁻ is BAF⁻, may be made by reacting acompound of formula (I) wherein Q is alkyl and S is halogen, with aboutone equivalent of an alkali metal salt, particularly the sodium salt, ofHBAF, in the presence of a coordinating ligand, particularly a nitrilesuch as acetonitrile. When X⁻ is an anion such as BAF⁻, SbF₆ ⁻ or BF₄ ⁻the same starting palladium compound can be reacted with the silver saltAgX.

However, sometimes the reaction of a diimine with a 1,5-COD Pd complexas described above to make compounds of formula (II) may be slow and/orgive poor conversions, thereby rendering it difficult to make thestarting material for (II) using the method described in the precedingparagraph. For instance when: R² ═R⁵ ═Ph₂ CH-- and R³ ═R⁴ ═H; R² ═R⁵═Ph-- and R³ ═R⁴ ═Ph; R² ═R⁵ ═2-t-butylphenyl and R³ ═R⁴ ═CH₃ ; R² ═R⁵═α-naphthyl and R³ ═R⁴ ═CH₃ ; and R² ═R² ═2-phenylphenyl and R³ ═R⁴ ═CH₃difficulty may be encountered in making a compound of formula (II).

In these instances it has been found more convenient to prepare (II) byreacting (η⁴ -1,5-COD)PdT⁻ Z!⁻ X⁻, wherein T¹ and X are as defined aboveand Z is an organic nitrile ligand, preferably in an organic nitrilesolvent, with a diimine of the formula ##STR55##

By a "nitrile solvent" is meant a solvent that is at least 20 volumepercent nitrile compound. The product of this reaction is (II), in whichthe Z ligand is the nitrile used in the synthesis. In a preferredsynthesis, T1 is methyl and the nitrile used is the same as in thestarting palladium compound, and is more preferably acetonitrile. Theprocess is carried out in solution, preferably when the nitrite issubstantially all of the solvent, at a temperature of about -40° C. toabout +60° C., preferably about 0° C. to about 30° C. It is preferredthat the reactants be used in substantially equimolar quantities.

The compound (η⁴ -1,5-COD)PdT¹ Z!⁺ X⁻, wherein T¹ is alkyl, Z is anorganic nitrile and X is a weakly coordinating anion may be made by thereaction of (η⁴ -1,5-COD)PdT¹ A, wherein A is Cl, Br or I and T¹ isalkyl with the silver salt of X⁻, AgX, or if X is BAF with an alkalimetal salt of HBAF, in the presence of an organic nitrile, which ofcourse will become the ligand T¹. In a preferred process A is Cl, T¹ isalkyl, more preferably methyl, and the organic nitrile is an alkylnitrile, more preferably acetonitrile. The starting materials arepreferably present in approximately equimolar amounts, except for thenitrile which is present preferably in excess. The solvent is preferablya non-coordinating solvent such as a halocarbon. Methylene chloride isuseful as such a solvent. The process preferably is carried out at atemperature of about -40° C. to about +50° C. It is preferred to excludewater and other hydroxyl containing compounds from the process, and thismay be done by purification of the ingredients and keeping the processmass under an inert gas such as nitrogen.

Compounds of formula (II) or (III) when the metal is nickel! can also bemade by the reaction of ##STR56## with a source of the conjugate acid ofthe anion X, the acid HX or its equivalent (such as a trityl salt) inthe presence of a solvent which is a weakly coordinating ligand such asa dialkyl ether or an alkyl nitrile. It is preferred to carry out thisreaction at about -80° C. to about 30° C.

Compounds of formula (XXXXI) can be made by a process, comprising,contacting, at a temperature of about -80° C. to about +20° C., acompound of the formula (η⁴ -1,5-COD)PdMe₂ and a diimine of the formula##STR57## wherein: COD is 1,5-cyclooctadiene; R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R⁷ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring. It ispreferred that the temperature is about -50° C. to about +10° C. It isalso preferred that the two starting materials be used in approximatelyequimolar quantities, and/or that the reaction be carried out insolution. It is preferred that R² and R⁵ are both 2-t-butylphenyl or2,5-di-t-butylphenyl and that R³ and R⁴ taken together are An, or R³ andR⁴ are both hydrogen or methyl.

Compounds of formula (IV) can be made by several routes. In one method acompound of formula (II) is reacted with an acrylate ester of theformula CH₂ ═CHCO₂ R¹ wherein R¹ is as defined above. This reaction iscarried out in a non-coordinating solvent such as methylene chloride,preferably using a greater than 1 to 50 fold excess of the acrylateester. In a preferred reaction, Q is methyl, and R¹ is alkyl containing1 to 4 carbon atoms, more preferably methyl. The process is carried outat a temperature of about -100° C. to about +100° C., preferably about0° C. to about 5020 . It is preferred to exclude water and otherhydroxyl containing compounds from the process, and this may be done bypurification of the ingredients and keeping the process mass under aninert gas such as nitrogen.

Alternatively, (IV) may be prepared by reacting (I), wherein Q is alkyland S is Cl, Er or I with a source of an appropriate weakly coordinatinganion such as AgX or an alkali metal salt of BAF and an acrylate ester(formula as immediately above) in a single step. Approximately equimolarquantities of (I) and the weakly coordinating anion source arepreferred, but the acrylate ester may be present in greater than 1 to 50fold excess. In a preferred reaction, Q is methyl, and R¹ is alkylcontaining 1 to 4 carbon atoms, more preferably methyl. The process ispreferably carried out at a temperature of about -100° C. to about +100°C., preferably about 0° C. to about 50° C. It is preferred to excludewater and other hydroxyl containing compounds from the process, and thismay be done by purification of the ingredients and keeping the processmass under an inert gas such as nitrogen.

In another variation of the preparation of (IV) from (I) the source ofthe weakly coordinating anion is a compound which itself does notcontain an anion, but which can combine with S of (I)! to form such aweakly coordinating anion. Thus in this type of process by "source ofweakly coordinating anion" is meant a compound which itself contains theanion which will become X⁻, or a compound which during the process cancombine with other process ingredients to form such an anion.

Catalysts of formula (V), wherein X⁻ is BAF⁻, may be made by reacting acompound of formula (I) wherein Q is alkyl and S is halogen, with aboutone-half of an equivalent of an alkali metal salt, particularly thesodium salt, of HBAF. Alternatively, (V) containing other anions may beprepared by reacting (I), wherein Q is alkyl and S is Cl, Br or I withone-half equivalent of a source of an appropriate weakly coordinatinganion such as AgX.

Some of the nickel and palladium compounds described above are useful inprocesses for polymerizing various olefins, and optionally alsocopolymerizing olefinic esters, carboxylic acids, or other functionalolefins, with these olefins. When (I) is used as a catalyst, a neutralLewis acid or a cationic Lewis or Bronsted acid whose counterion is aweakly coordinating anion is also present as part of the catalyst system(sometimes called a "first compound" in the claims). By a "neutral Lewisacid" is meant a compound which is a Lewis acid capable for abstractingQ⁻ or S⁻ from (I) to form a weakly coordination anion. The neutral Lewisacid is originally uncharged (i.e., not ionic). Suitable neutral Lewisacids include SbF₅, Ar₃ B (wherein Ar is aryl), and BF₃. By a cationicLewis acid is meant a cation with a positive charge such as Ag⁺, H⁺, andNa⁺.

In those instances in which (I) (and similar catalysts which require thepresence of a neutral Lewis acid or a cationic Lewis or Bronsted acid),does not contain an alkyl or hydride group already bonded to the metal(i.e., neither Q or S is alkyl or hydride), the neutral Lewis acid or acationic Lewis or Bronsted acid also alkylates or adds a hydride to themetal, i.e., causes an alkyl group or hydride to become bonded to themetal atom.

A preferred neutral Lewis acid, which can alkylate the metal, is aselected alkyl aluminum compound, such as R⁹ ₃ Al, R⁹ ₂ AlCl, R⁹ AlCl₂,and "R⁹ AlO" (alkylaluminoxanes), wherein R⁹ is alkyl containing 1 to 25carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminumcompounds include methylaluminoxane (which is an oligomer with thegeneral formula MeAlO!_(n)), (C₂ H₅)₂ AlCl, C₂ H₅ AlCl₂, and (CH₃)₂CHCH₂ !₃ Al.

Metal hydrides such as NaBH₄ may be used to bond hydride groups to themetal M.

The first compound and (I) are contacted, usually in the liquid phase,and in the presence of the olefin, and/or 4-vinylcyclohexene,cyclopentene, cyclobutene, substituted norbornene, or norbornene. Theliquid phase may include a compound added just as a solvent and/or mayinclude the monomer(s) itself. The molar ratio of first compound:nickelor palladium complex is about 5 to about 1000, preferably about 10 toabout 100. The temperature at which the polymerization is carried out isabout -100° C. to about +200° C., preferably about -200° C. to about+80° C. The pressure at which the polymerization is carried out is notcritical, atmospheric pressure to about 275 MPa, or more, being asuitable range. The pressure may affect the microstructure of thepolyolefin produced (see below).

When using (I) as a catalyst, it is preferred that R³ and R⁴ arehydrogen, methyl, or taken together are ##STR58## It is also preferredthat both R² and R⁵ are 2,6-diisopropylphenyl, 2,6-dimethylphenyl,2,6-diethylphenyl, 4-methylphenyl, phenyl, 2,4,6-trimethylphenyl, and2-t-butylphenyl. When M is Ni(II), it is preferred that Q and S are eachindependently chloride or bromide, while when M is Pd(II) it ispreferred that Q is methyl, chloride, or bromide, and S is chloride,bromide or methyl. In addition, the specific combinations of groups inthe catalysts listed in Table I are especially preferred.

                  TABLE I    ______________________________________    R.sup.2   R.sup.3                    R.sup.5 R.sup.5  Q     S   M    ______________________________________    2,6-i-PrPh              H     H       2,6-i-PrPh                                     Me    Cl  Pd    2,6-i-PrPh              Me    Me      2,6-i-PrPh                                     Me    Cl  Pd    2,6-i-PrPh              An    An      2,6-i-PrPh                                     Me    Cl  Pd    2,6-MePh  H     H       2,6-MePh Me    Cl  Pd    4-MePh    H     H       4-MePh   Me    Cl  Pd    4-MePh    Me    Me      4-MePh   Me    Cl  Pd    2,6-i-PrPh              Me    Me      2,6-i-PrPh                                     Me    Me  Pd    2,6-i-PrPh              H     H       2,6-i-PrPh                                     Me    Me  Pd    2,6-MePh  H     H       2,6-MePh Me    Me  Pd    2,6-i-PrPh              H     H       2,6-i-PrPh                                     Br    Br  Ni    2,6-i-PrPh              Me    Me      2,6-i-PrPh                                     Br    Br  Ni    2,6-MePh  H     H       2,6-MePh Br    Br  Ni    Ph        Me    Me      Ph       Me    Cl  Pd    2,6-EtPh  Me    Me      2,6-EtPh Me    Cl  Pd    2,4,6-MePh              Me    Me      2,4,6-MePh                                     Me    Cl  Pd    2,6-MePh  Me    Me      2,6-MePh Br    Br  Ni    2,6-i-PrPh              An    An      2,6-i-PrPh                                     Br    Br  Ni    2,6-MePh  An    An      2,6-MePh Br    Br  Ni    2-t-BuPh  An    An      2-t-BuPh Br    Br  Ni    2,5-t-BuPh              An    An      2,5-t-BuPh                                     Br    Br  Ni    2-i-Pr-6-MePh              An    An      2-i-Pr-6-MePh                                     Br    Br  Ni    2-i-Pr-6-MePh              Me    Me      2-i-Pr-6-MePh                                     Br    Br  Ni    2,6-t-BuPh              H     H       2,6-t-BuPh                                     Br    Br  Ni    2,6-t-BuPh              Me    Me      2,6-t-BuPh                                     Br    Br  Ni    2,6-t-BuPh              An    An      2,6-t-BuPh                                     Br    Br  Ni    2-t-BuPh  Me    Me      2-t-BuPh Br    Br  Ni    ______________________________________

Note--In Tables I and II, and elsewhere herein, the following conventionand abbreviations are used. For R² and R⁵, when a substituted phenylring is present, the amount of substitution is indicated by the numberof numbers indicating positions on the phenyl ring, so that, forexample, 2,6-i-PrPh is 2,6-diisopropylphenyl. The followingabbreviations are used: i-Pr=isopropyl; Me=methyl; Et=ethyl;t-Bu=t-butyl; Ph=phenyl; Np=naphthyl; An=1,8-naphthylene (a divalentradical used for both R³ and R⁴, wherein R³ and R⁴ taken together form aring, which is part of an acenaphthylene group); OTf=triflate; andBAF=tetrakis 3,5-bis(trifluoromethyl)phenyl!borate.

Preferred olefins in the polymerization are one or more of ethylene,propylene, 1-butene, 2-butene, 1-hexene 1-octene, 1-pentene,1-tetradecene, norbornene, and cyclopentene, with ethylene, propyleneand cyclopentene being more preferred. Ethylene (alone as a homopolymer)is especially preferred.

The polymerizations with (I) may be run in the presence of variousliquids, particularly aprotic organic liquids. The catalyst system,monomer(s), and polymer may be soluble or insoluble in these liquids,but obviously these liquids should not prevent the polymerization fromoccurring. Suitable liquids include alkanes, cycloalkanes, selectedhalogenated hydrocarbons, and aromatic hydrocarbons. Specific usefulsolvents include hexane, toluene and benzene.

Whether such a liquid is used, and which and how much liquid is used,may affect the product obtained. It may affect the yield,microstructure, molecular weight, etc., of the polymer obtained.

Compounds of formulas (XI), (XIII), (XV) and (XIX) may also be used ascatalysts for the polymerization of the same monomers as compounds offormula (I). The polymerization conditions are the same for (XI),(XIII), (XV) and (XIX) as for (I), and the same Lewis and Bronsted acidsare used as co-catalysts. Preferred groupings R², R³, R⁴, and R⁵ (whenpresent) in (XI) and (XIII) are the same as in (I), both in apolymerization process and as compounds in their own right.

Preferred (XI) compounds have the metals Sc(III), Zr(IV), Ni (II),Ni(I), Pd(II), Fe(II), and Co(II). When M is Zr, Ti, Fe, and Sc it ispreferred that all of Q and S are chlorine or bromine more preferablychlorine. When M is Ni or Co it is preferred that all of Q and S arechlorine, bromine or iodine, more preferably bromine.

In (XVII) preferred metals are Ni(II) and Ti(IV). It is preferred thatall of Q and S are halogen. It is also preferred that all of R²⁸, R²⁹,and R³⁰ are hydrogen, and/or that both R⁴⁴ and R⁴⁵ are2,4,6-trimethylphenyl or 9-anthracenyl.

In (XV) it is preferred that both of R³¹ are hydrogen.

In (XIII), (XXIII) and (XXXII) (as polymerization catalysts and as novelcompounds) it is preferred that all of R²⁰, R²¹, R²² and R²³ are methyl.It is also preferred that T¹ and T² are methyl. For (XIII), when M isNi(I) or (II), it is preferred that both Q and S are bromine, while whenM is Pd it is preferred that Q is methyl and S is chlorine.

Compounds (II), (IV) or (VII) will each also cause the polymerization ofone or more of an olefin, and/or a selected cyclic olefin such ascyclobutene, cyclopentene or norbornene, and, when it is a Pd(II)complex, optionally copolymerize an ester or carboxylic acid of theformula CH₂ ═CH(CH₂)_(m) CO₂ R¹, wherein m is 0 or an integer of 1 to 16and R¹ is hydrogen or hydrocarbyl or substituted hydrocarbyl, bythemselves (without cocatalysts). However, (III) often cannot be usedwhen the ester is present. When norbornene or substituted norbornene ispresent no other monomer should be present.

Other monomers which may be used with compounds (II), (IV) or (VII)(when it is a Pd(II) complex) to form copolymers with olefins andselected cycloolefins are carbon monoxide (CO), and vinyl ketones of thegeneral formula H₂ C═CHC(O)R²⁵, wherein R²⁵ is alkyl containing 1 to 20carbon atoms, and it is preferred that R²⁵ is methyl. In the case of thevinyl ketones, the same compositional limits on the polymers producedapply as for the carboxylic acids and esters described as comonomers inthe immediately preceding paragraph.

CO forms alternating copolymers with the various olefins andcycloolefins which may be polymerized with compounds (II), (IV) or(VII). The polymerization to form the alternating copolymers is donewith both CO and the olefin simultaneously in the process mixture, andavailable to the catalyst. It is also possible to form block copolymerscontaining the alternating CO/(cyclo)olefin copolymers and other blockscontaining just that olefin or other olefins or mixtures thereof. Thismay be done simply by sequentially exposing compounds (II), (IV) or(VII), and their subsequent living polymers, to the appropriate monomeror mixture of monomers to form the desired blocks. Copolymers of CO, a(cyclo)olefin and a saturated carboxylic acid or ester of the formulaCH₂ ═CH(CH₂)_(m) CO₂ R¹, wherein m is 0 or an integer of 1 to 16 and R¹is hydrogen or hydrocarbyl or substituted hydrocarbyl, may also be madeby simultaneously exposing the polymerization catalyst or living polymerto these 3 types of monomers.

The polymerizations may be carried out with (II), (III), (IV) or (VII),and other catalyst molecules or combinations, initially in the solidstate assuming (II), (III) (IV) or (VII) is a solid! or in solution. Theolefin and/or cycloolefin may be in the gas or liquid state (includinggas dissolved in a solvent). A liquid, which may or may not be a solventfor any or all of the reactants and/or products may also be present.Suitable liquids include alkanes, cycloalkanes, halogenated alkanes andcycloalkanes, ethers, water, and alcohols, except that when (III) isused, hydrocarbons should preferably be used as solvents. Specificuseful solvents include methylene chloride, hexane, CO₂, chloroform,perfluoro(n-butyltetrahydrofuran) (herein sometimes called FC-75),toluene, dichlorobenzene, 2-ethylhexanol, and benzene.

It is particularly noteworthy that one of the liquids which can be usedin this polymerization process with (II), (III), (IV) or (VII) is water,see for instance Examples 213-216. Not only can water be present but thepolymerization "medium" may be largely water, and various types ofsurfactants may be employed so that an emulsion polymerization may bedone, along with a suspension polymerization when surfactants are notemployed.

Preferred olefins and cycloolefins in the polymerization using (II),(III) or (IV) are one or more of ethylene, propylene, 1-butene,1-hexene, 1-octene, 1-butene, cyclopentene, 1-tetradecene, andnorbornene; and ethylene, propylene and cyclopentene are more preferred.Ethylene alone is especially preferred.

Olefinic esters or carboxylic acids of the formula CH₂ ═CH(CH₂)_(m) CO₂R², wherein R¹ is hydrogen, hydrocarbyl, or substituted hydrocarbyl, andm is 0 or an integer of 1 to 16. It is preferred if R¹ hydrocarbyl orsubstituted hydrocarbyl and it is more preferred if it is alkylcontaining 1 to 10 carbon atoms, or glycidyl. It is also preferred if mis 0 and/or R¹ is alkyl containing 1 to 10 carbon atoms. It is preferredto make copolymers containing up to about 60 mole percent, preferably upto about 20 mole percent of repeat units derived from the olefinic esteror carboxylic acid. Total repeat unit units in the polymer herein refernot only to those in the main chain from each monomer unit, but those inbranches or side chains as well.

When using (II), (III), (IV) or (VII) as a catalyst it is preferred thatR³ and R⁴ are hydrogen, methyl, or taken together are ##STR59## It isalso preferred that both R² and R⁵ are 2,6-diisopropylphenyl,2,6-dimethylphenyl, 4-methylphenyl, phenyl, 2,6-diethylphenyl,2,4,6-trimethylphenyl and 2-t-butylphenyl. When (II) is used, it ispreferred that T¹ is methyl, R⁶ is methyl or ethyl and R⁷ is methyl.When (III) is used it is preferred that T¹ is methyl and said Lewis baseis R⁶ ₂ O, wherein R⁶ is methyl or ethyl. When (IV) is used it ispreferred that R⁸ is methyl, n is 3 and R¹⁶ is hydrogen. In addition inTable II are listed all particularly preferred combinations as catalystsfor (II), (III), (IV) and (VII).

                                      TABLE II    __________________________________________________________________________    Compound    Type  R.sup.2                R.sup.3                  R.sup.4                    R.sup.5                          T.sup.1 /T.sup.2 /R.sup.8                               Z   M X    __________________________________________________________________________    (II)  2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   OEt.sub.2                                   Pd                                     BAF    (II)  2,6-i-PrPh                H H 2,6-i-PrPh                          Me   OEt.sub.2                                   Pd                                     BAF    (III) 2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   OEt.sub.2                                   Ni                                     BAF    (III) 2,6-i-PrPh                H H 2,6-i-PrPh                          Me   OEt.sub.2                                   Ni                                     BAF    (II)  2,6-MePh                H H 2,6-MePh                          Me   OEt.sub.2                                   Pd                                     BAF    (II)  2,6-MePh                Me                  Me                    2,6-MePh                          Me   OEt.sub.2                                   Pd                                     BAF    (II)  2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   OEt.sub.2                                   Pd                                     SbF.sub.6    (II)  2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   OEt.sub.2                                   Pd                                     BF.sub.4    (II)  2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   OEt.sub.2                                   Pd                                     PF.sub.6    (II)  2,6-i-PrPh                H H 2,6-i-PrPh                          Me   OEt.sub.2                                   Pd                                     SbF.sub.6    (II)  2,4,6-MePh                Me                  Me                    2,4,6-MePh                          Me   OEt.sub.2                                   Pd                                     SbF.sub.6    (II)  2,6-i-PrPh                An                  An                    2,6-i-PrPh                          Me   OEt.sub.2                                   Pd                                     SbF.sub.6    (II)  2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   NCMe                                   Pd                                     SbF.sub.6    (II)  Ph    Me                  Me                    Ph    Me   NCMe                                   Pd                                     SbF.sub.6    (II)  2,6-EtPh                Me                  Me                    2,6-EtPh                          Me   NCMe                                   Pd                                     BAF    (II)  2,6-EtPh                Me                  Me                    2,6-EtPh                          Me   NCMe                                   Pd                                     SbF.sub.6    (II)  2-t-BuPh                Me                  Me                    2-t-BuPh                          Me   NCMe                                   Pd                                     SbF.sub.6    (II)  1-Np  Me                  Me                    1-Np  Me   NCMe                                   Pd                                     SbF.sub.6    (II)  Ph.sub.2 CH                H H Ph.sub.2 CH                          Me   NCMe                                   Pd                                     SbF.sub.6    (II)  2-PhPh                Me                  Me                    2-PhPh                          Me   NCMe                                   Pd                                     SbF.sub.6    (II)  Ph    .sup.a                  .sup.a                    Ph    Me   NCMe                                   Pd                                     BAF    (IV)  2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   .sup.b                                   Pd                                     SbF.sub.6    (IV)  2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   .sup.b                                   Pd                                     BAF    (IV)  2,6-i-PrPh                H H 2,6-i-PrPh                          Me   .sup.b                                   Pd                                     SbF.sub.6    (IV)  2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   .sup.b                                   Pd                                     B(C.sub.6 F.sub.5).sub.3 Cl    (II)  Ph    Me                  Me                    Ph    Me   NCMe                                   Ph                                     SbF.sub.6    (VII) 2,6-i-PrPh                Me                  Me                    2,6-i-PrPh                          Me   --  Pd                                     OTf    (II)  Ph    Ph                  Ph                    Ph    Me   NCMe                                   Pd                                     BAF    (II)  Ph.sub.2 CH                H H Ph.sub.2 CH                          Me   NCMe                                   Pd                                     SbF.sub.6    __________________________________________________________________________     .sup.a This group is --CMe.sub.2 CH.sub.2 CMe.sub.2     .sup.b This group is --(CH.sub.2).sub.3 CO.sub.2 Me

When using (II), (III), (IV) or (VII) the temperature at which thepolymerization is carried out is about -100° C. to about +20° C.,preferably about 0° C. to about 150° C., more preferably about 25° C. toabout 100° C. The pressure at which the polymerization is carried out isnot critical, atmospheric pressure to about 275 MPa being a suitablerange. The pressure can affect the microstructure of the polyolefinproduced (see below).

Catalysts of the formulas (II), (III), (IV) and (VII) may also besupported on a solid catalyst (as opposed to just being added as a solidor in solution), for instance on silica gel (see Example 98). Bysupported is meant that the catalyst may simply be carried physically onthe surface of the solid support, may be adsorbed, or carried by thesupport by other means.

When using (XXX) as a ligand or in any process or reaction herein it ispreferred that n is 2, all of R³⁰, R²⁸ and R²⁹ are hydrogen, and both ofR⁴⁴ and R⁴⁵ are 9-anthracenyl.

Another polymerization process comprises contacting a compound of theformula Pd(R¹³ CN)₄ !X₂ or a combination of Pd OC(O)R⁴⁰ !₂ and HX, witha compound of the formula ##STR60## and one or more monomers selectedfrom the group consisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclopentene, cyclobutene, substitutednorbornene and norbornene, wherein: R² and R⁵ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound to the imino nitrogen atom has at least two carbon atoms bound toit; R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a carbocyclic ring; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that R¹⁷contains no olefinic bonds; R⁴⁰ is hydrocarbyl or substitutedhydrocarbyl; and X is a weakly coordinating anion; provided that whennorbornene or substituted norbornene is present no other monomer ispresent.

It is believed that in this process a catalyst similar to (II) may beinitially generated, and this then causes the polymerization. Therefore,all of the conditions, monomers (including olefinic esters andcarboxylic acids), etc., which are applicable to the process using (II)as a polymerization catalyst are applicable to this process. Allpreferred items are also the same, including appropriate groups such asR², R³, R⁴, R⁵, and combinations thereof. This process however should berun so that all of the ingredients can contact each other, preferably ina single phase. Initially at least, it is preferred that this is done insolution. The molar ratio of (VIII) to palladium compound used is notcritical, but for most economical use of the compounds, a moderateexcess, about 25 to 100% excess, of (VIII) is preferably used.

As mentioned above, it is believed that in the polymerization using(VIII) and Pd(R¹³ CN)₄ !X₂ or a Pd II! carboxylate a catalyst similar to(II) is formed. Other combinations of starting materials that cancombine into catalysts similar to (II), (III), (IV) and (VII) often alsocause similar polymerizations, see for instance Examples 238 and 239.Also combinations of α-diimines or other diimino ligands describedherein with: a nickel 0! or nickel rip compound, oxygen, an alkylaluminum compound and an olefin; a nickel 0! or nickel I! compound, anacid such as HX and an olefin; or an α-diimine Ni 0! or nickel I!complex, oxygen, an alkyl aluminum compound and an olefin. Thus activecatalysts from α-diimines and other bidentate imino compounds can beformed beforehand or in the same "pot" (in situ) in which thepolymerization takes place. In all of the polymerizations in which thecatalysts are formed in situ, preferred groups on the α-diimines are thesame as for the preformed catalysts.

In general Ni 0!, Ni I! or Ni(II) compounds may be used as precursors toactive catalyst species. They must have ligands which can be displacedby the appropriate bidentate nitrogen ligand, or must already containsuch a bidentate ligand already bound to the nickel atom. Ligands whichmay be displaced include 1,5-cyclooctadiene and tris(o-tolyl)phosphite,which may be present in Ni 0! compounds, or dibenzylideneacetone, as inthe useful Pd 0! precursor tris(dibenzylideneacetone)dipalladium 0!.These lower valence nickel compounds are believed to be converted intoactive Ni II! catalytic species. As such they must also be contacted(react with) with an oxidizing agent and a source of a weaklycoordinating anion (X⁻). Oxidizing agents include oxygen, HX (wherein Xis a weakly coordinating anion), and other well known oxidizing agents.Sources of X⁻ include HX, alkylaluminum compounds, alkali metal andsilver salts of X⁻. As can be seen above, some compounds such as HX mayact as both an oxidizing agent and a source of X⁻. Compounds containingother lower valent metals may be converted into active catalyst speciesby similar methods.

When contacted with an alkyl aluminum compound or HX useful Ni 0!compounds include ##STR61##

Various types of Ni 0! compounds are known in the literature. Below arelisted references for the types shown immediately above.

(XXXIII) G. van Koten, et al., Adv. Organometal. Chem., vol. 21, p.151-239 (1982).

(XXXXII) W. Bonrath, et al., Angew. Chem. Int. Ed. Engl., Vol. 29, p.298-300 (1990).

(XXXXIV) H. tom Dieck, et al., Z. Natruforsch., vol. 366, p. 823-832(1981); and M. Svoboda, et al., J. Organometal. Chem., vol. 191, p.321-328 (1980).

(XXXXV) G. van Koten, et al., Adv. Organometal. Chem., vol. 21, p.151-239 (1982).

In polymerizations using (XIV), the same preferred monomers and groups(such as R², R³, R⁴, R⁵ and X) as are preferred for the polymerizationusing (II) are used and preferred. Likewise, the conditions used andpreferred for polymerizations with (XIV) are similar to those used andpreferred for (II), except that higher olefin pressures (when the olefinis a gas) are preferred. Preferred pressures are about 2.0 to about 20MPa. (XIV) may be prepared by the reaction of one mole of Pd(R¹³ CN)₄!X₂ with one mole of (VIII) in acetonitrile or nitromethane.

Novel compound (XIV) is used as an olefin polymerization catalyst. Inpreferred forms of (XIV), the preferred groups R², R³, R⁴, R⁵ and X arethe same as are preferred for compound (II).

Another type of compound which is an olefin polymerization catalyst areπ-allyl and π-benzyl compounds of the formula ##STR62## wherein M isNi(II) or Pd(II); R² and R⁵ are hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound directly to the imino nitrogen atomhas at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a ring; X is a weakly coordinating anion; and A is a π-allyl orπ-benzyl group. By a π-allyl group is meant a monoanionic with 3adjacent sp² carbon atoms bound to a metal center in an η³ fashion. Thethree sp² carbon atoms may be substituted with other hydrocarbyl groupsor functional groups. Typical π-allyl groups include ##STR63## wherein Ris hydrocarbyl. By a π-benzyl group is meant π-allyl ligand in which twoof the sp² carbon atoms are part of an aromatic ring. Typical π-benzylgroups include ##STR64## π-Benzyl compounds usually initiatepolymerization of the olefins fairly readily even at room temperature,but π-allyl compounds may not necessarily do so. Initiation of n-allylcompounds can be improved by using one or more of the following methods:

Using a higher temperature such as about

Decreasing the bulk of the α-diimine ligand, such as R² and R⁵ being2,6-dimethylphenyl instead of 2,6-diisopropylphenyl.

Making the π-allyl ligand more bulky, such as using ##STR65## ratherthan the simple π-allyl group itself. Having a Lewis acid present whileusing a functional π-allyl or π-benzyl group. Relatively weak Lewisacids such a triphenylborane, tris(pentafluorophenyl)borane, andtris(3,5-trifluoromethylphenyl)borane, are preferred. Suitablefunctional groups include chloro and ester. "Solid" acids such asmontmorillonite may also be used.

When using (XXXVII) as a polymerization catalyst, it is preferred thatethylene and/or a linear α-olefin is the monomer, or cyclopentene, morepreferred if the monomer is ethylene and/or propylene, and ethylene isespecially preferred. A preferred temperature for the polymerizationprocess using (XXXVII) is about +20° C. to about 100° C. It is alsopreferred that the partial pressure due to ethylene or propylene monomeris at least about 600 kPa. It is also noted that (XXXVII) is a novelcompound, and preferred items for (XXXVII) for the polymerizationprocess are also preferred for the compound itself.

Another catalyst for the polymerization of olefins is a compound of theformula ##STR66## and one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene,

wherein: R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; R⁵⁴ is hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; eachR⁵⁵ is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, ora functional group; W is alkylene or substituted alkylene containing 2or more carbon atoms; Z is a neutral Lewis base wherein the donatingatom is nitrogen, sulfur, or oxygen, provided that if the donating atomis nitrogen then the pKa of the conjugate acid of that compound(measured in water) is less than about 6, or an olefin of the formulaR¹⁷ CH═CHR¹⁷ ; each R¹⁷ is independently alkyl or substituted alkyl; andX is a weakly coordinating anion. It is preferred that in compound(XXXVIII) that: R⁵⁴ is phenyl or substituted phenyl, and preferredsubstituents are alkyl groups; each R⁵⁵ is independently hydrogen oralkyl containing 1 to 10 carbon atoms; W contains 2 carbon atoms betweenthe phenyl ring and metal atom it is bonded to or W is a divalentpolymeric group derived from the polymerization of R¹⁷ CH═CHR¹⁷, and itis especially preferred that it is --CH(CH₃)CH₂ -- or --C(CH₃)₂ CH₂ --;and Z is a dialkyl ether or an olefin of the formula R¹⁷ CH═CHR¹⁷ ; andcombinations thereof. W is an alkylene group in which each of the twofree valencies are to different carbon atoms of the alkylene group.

When W is a divalent group formed by the polymerization of R¹⁷ CH═CHR¹⁷,and Z is R¹⁷ CH═CHR¹⁷, the compound (XXXVIII) is believed to be a livingended polymer. That end of W bound to the phenyl ring actually is theoriginal fragment from R⁵⁶ from which the "bridge" W originally formed,and the remaining art of W is formed from the olefin(s) R¹⁷ CH═CHR¹⁷. Ina sense this compound is similar in function to compound (VI).

By substituted phenyl in (XXXVIII) and (XXXIX) is meant the phenyl ringcan be substituted with any grouping which does not interfere with thecompound's stability or any of the reactions the compound undergoes.Preferred substituents in substituted phenyl are alkyl groups,preferably containing 1 to 10 carbon atoms.

Preferred monomers for this polymerization are ethylene and linearα-olefins, or cyclopentene, particularly propylene, and ethylene andpropylene or both are more preferred, and ethylene is especiallypreferred.

It is noted that (XXXVIII) is a novel compound, and preferred compoundsand groupings are the same as in the polymerization process.

Compound (XXXVIII) can be made by heating compound (XXXIX), ##STR67##wherein: R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; R is hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; eachR⁵⁵ is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, ora functional group; R⁵⁶ is alkyl containing 2 to 30 carbon atoms; T³ isalkyl; Z is a neutral Lewis base wherein the donating atom is nitrogen,sulfur, or oxygen, provided that if the donating atom is nitrogen thenthe pKa of the conjugate acid of that compound (measured in water) isless than about 6; and X is a weakly coordinating anion. Preferredgroups are the same as those in (XXXVIII). In addition it is preferredthat T⁵ contain 1 to 10 carbon atoms, and more preferred that it ismethyl. A preferred temperature for the conversion of (XXXIX) to(XXXVIII) is about -30° C. to about 50° C. Typically the reaction takesabout 10 min. to about 5 days, the higher the temperature, the fasterthe reaction. Another factor which affects the reaction rate is thenature of Z. The weaker the Lewis basicity of Z, the faster the desiredreaction will be.

When (II), (III), (IV), (V), (VII), (VIII) or a combination of compoundsthat will generate similar compounds, (subject to the conditionsdescribed above) is used in the polymerization of olefins, cyclolefins,and optionally olefinic esters or carboxylic acids, polymer having whatis believed to be similar to a "living end" is formed. This molecule isthat from which the polymer grows to its eventual molecular weight. Thiscompound may have the structure ##STR68## wherein: M is Ni(II) orPd(II); R² and R⁵ are hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound directly to the imino nitrogen atom has atleast two carbon atoms bound to it; R³ and R⁴ are each independentlyhydrogen, hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ takentogether are hydrocarbylene or substituted hydrocarbylene to form aring; each R¹¹ is independently hydrogen, alkyl or --(CH₂)_(m) CO₂ R¹ ;T³ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ (C═O)--, R¹⁵ O(C═O)--, or --CH₂ CH₂ CH₂ CO₂ R⁸ ; R¹⁵ is hydrocarbylnot containing olefinic or acetylenic unsaturation; P is a divalentgroup containing one or more repeat units derived from thepolymerization of one or more of ethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, or norbornene and, when M is Pd(II), optionally one or morecompounds of the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹ ; R⁸ is hydrocarbyl;each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; m is 0 or an integer from 1 to 16; R¹is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to10 carbon atoms; and X is a weakly coordinating anion; and that when Mis Ni(II), R¹¹ is not --CO₂ R⁸ and when M is Pd a diene is not present.By an "olefinic ester or carboxylic acid" is meant a compound of theformula CH₂ ═CH(CH₂)_(m) CO₂ R¹, wherein m and R¹ are as definedimmediately above.

This molecule will react with additional monomer (olefin, cyclic olefin,olefinic ester or olefinic carboxylic acid) to cause furtherpolymerization. In other words, the additional monomer will be added toP, extending the length of the polymer chain. Thus P may be of any size,from one "repeat unit" to many repeat units, and when the polymerizationis over and P is removed from M, as by hydrolysis, P is essentially thepolymer product of the polymerization. Polymerizations with (VI), thatis contact of additional monomer with this molecule takes place underthe same conditions as described above for the polymerization processusing (II), (III), (IV), (V), (VII) or (VIII), or combinations ofcompounds that will generate similar molecules, and where appropriatepreferred conditions and structures are the same.

The group T³ in (VI) was originally the group T¹ in (II) or (III), orthe group which included R⁸ in (IV). It in essence will normally be oneof the end groups of the eventual polymer product. The olefinic groupwhich is coordinated to M, R¹¹ CH═CHR¹¹ is normally one of the monomers,olefin, cyclic olefin, or, if Pd(II) is M, an olefinic ester orcarboxylic acid. If more than one of these monomers is present in thereaction, it may be any one of them. It is preferred that T³ is alkyland especially preferred that it is methyl, and it is also preferredthat R¹¹ is hydrogen or n-alkyl. It is also preferred that M is Pd(II).

Another "form" for the living end is (XVI). ##STR69## This type ofcompound is sometimes referred to as a compound in the "agostic state".In fact both (VI) and (XVI) may coexist together in the samepolymerization, both types of compound representing living ends. It isbelieved that (XVI)-type compounds are particularly favored when the endof the growing polymer chain bound to the transition metal is derivedfrom a cyclic olefin such as cyclopentene. Expressed in terms of thestructure of (XVI) this is when both of R¹¹ are hydrocarbylene to form acarbocyclic ring, and it is preferred that this be a five-memberedcarbocyclic ring.

For both the polymerization process using (XVI) and the structure of(XVI) itself, the same conditions and groups as are used and preferredfor (VI) are also used and preferred for (XVI), with the exception thatfor R¹¹ it is preferred in (XVI) that both of R¹¹ are hydrocarbylene toform a carbocyclic ring.

This invention also concerns a compound of one formula ##STR70##wherein: M is Ni(II) or Pd(II); R² and R⁵ are hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound directly to the iminonitrogen atom has at least two carbon atoms bound to it; R³ and R⁴ areeach independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R³and R⁴ taken together are hydrocarbylene or substituted hydrocarbyleneto form a ring; each R¹⁴ is independently hydrogen, alkyl or when M isPd(II)!--(CH₂)_(m) CO₂ R¹ ; R¹ is hydrogen, or hydrocarbyl orsubstituted hydrocarbyl containing 1 to 10 carbon atoms; T⁴ is alkyl,--R⁶⁰ C(O)OR⁸, R¹⁵ (C═O)-- or R¹⁵ OC(═O)--; R¹⁵ is hydrocarbyl notcontaining olefinic or acetylenic bonds; R⁶⁰ is alkylene not containingolefinic or acetylenic bonds; R⁸ is hydrocarbyl; and X is a weaklycoordinating anion.

(IX) may also be used to polymerize olefins, cyclic olefins, andoptionally olefinic esters and carboxylic acids. The same conditions(except as noted below) apply to the polymerizations using (IX) as theydo for (VI). It is preferred that M is Pd(II) and T⁴ is methyl.

A compound of formula (V) may also be used as a catalyst for thepolymerization of olefins, cyclic olefins, and optionally olefinicesters and/or carboxylic acids. In this process (V) is contacted withone or more of the essential monomers. Optionally a source of arelatively weakly coordinating anion may also be present. Such a sourcecould be an alkali metal salt of BAF or AgX (wherein X is the anion),etc. Preferably about 1 mole of the source of X, such as AgX, will beadded per mole of (V). This will usually be done in the liquid phase,preferably in which (V) and the source of the anion are at leastpartially soluble. The conditions of this polymerization are otherwisethe same as described above for (II), (III), (IV) and (VII), includingthe preferred conditions and ingredients.

In polymerizations using (XX) as the catalyst, a first compound which isa source of a relatively noncoordinating monoanion is present. Such asource can be an alkali metal or silver salt of the monoanion. ##STR71##It is preferred that the alkali metal cation is sodium or potassium. Itis preferred that the monoanion is SbF₆ ³¹, BAF, PF₆ ³¹, or BF₄ ⁻, andmore preferred that it is BAF. It is preferred that T¹ is methyl and/orS is chlorine. All other preferred groups and conditions for thesepolymerizations are the same as for polymerizations with (II).

In all of the above polymerizations, and the catalysts for making themit is preferred that R² and R⁵, if present, are 2,6-diisopropylphenyland R³ and R⁴ are hydrogen or methyl. When cyclopentene is polymerized,is preferred that R² and R⁵ (if present) are 2,6-dimethylphenyl or2,4,6-trimethylphenyl and that R³ and R⁴ taken together are An. R², R³,R⁴ and R⁵ and other groups herein may also be substituted hydrocarbyl.As previously defined, the substituent groups in substituted hydrocarbylgroups (there may be one or more substituent groups) should notsubstantially interfere with the polymerization or other reactions thatthe compound is undergoing. Whether a particular group will interferecan first be judged from the artisans general knowledge and theparticular polymerization or other reaction that is involved. Forinstance, in polymerizations where an alkyl aluminum compound is usedmay not be compatible with the presence of groups containing an active(relatively acidic) hydrogen atom, such as hydroxyl or carboxyl becauseof the known reaction of alkyl aluminum compounds with such activehydrogen containing groups (but such polymerizations may be possible ifenough "extra" alkyl aluminum compound is added to react with thesegroups). However, in very similar polymerizations where alkyl aluminumcompounds are not present, these groups containing active hydrogen maybe present. Indeed many of the polymerization processes described hereinare remarkably tolerant to the presence of various functional groups.Probably the most important considerations as to the operability ofcompounds containing any particular functional group are the effect ofthe group on the coordination of the metal atom (if present), and sidereaction of the group with other process ingredients (such as notedabove). Therefore of course, the further away from the metal atom thefunctional group is, the less likely it is to influence, say, apolymerization. If there is doubt as to whether a particular functionalgroup, in a particular position, will affect a reaction, simple minimalexperimentation will provide the requisite answer. Functional groupswhich may be present in R², R³, R⁴, R⁵, and other similar radicalsherein include hydroxy, halo (fluoro, chloro, bromo and iodo), ether,ester, dialkylamino, carboxy, oxo (keto and aldehyo), nitro, amide,thioether, and imino. Preferred functional groups are hydroxy, halo,ether and dialkylamino.

Also in all of the polymerizations, the (cyclo)olefin may be substitutedhydrocarbyl. Suitable substituents include ether, keto, aldehyde, ester,carboxylic acid.

In all of the above polymerizations, with the exceptions noted below,the following monomer(s), to produce the corresponding homo- orcopolymers, are preferred to be used: ethylene; propylene; ethylene andpropylene; ethylene and an α-olefin; an α-olefin; ethylene and an alkylacrylate, especially methyl acrylate; ethylene and acrylic acid;ethylene and carbon monoxide; ethylene, and carbon monoxide and anacrylate ester or acrylic acid, especially methyl acrylate; propyleneand alkyl acrylate, especially methyl acrylate; cyclopentene;cyclopentene and ethylene; cyclopentene and propylene. Monomers whichcontain a carbonyl group, including esters, carboxylic acids, carbonmonoxide, vinyl ketones, etc., can be polymerized with Pd(II) containingcatalysts herein, with the exception of those that require the presenceof a neutral or cationic Lewis acid or cationic Bronsted acid, which isusually called the "first compound" in claims describing suchpolymerization processes.

Another useful "monomer" for these polymerization processes is a C₄refinery catalytic cracker stream, which will often contain a mixture ofn-butane, isobutane, isobutene, 1-butene, 2-butenes and small; amountsof butadiene. This type of stream is referred to herein as a "crudebutenes stream". This stream may act as both the monomer source and"solvent" for the polymerization. It is preferred that the concentrationof 1- and 2-butenes in the stream be as high as possible, since theseare the preferred compounds to be polymerized. The butadiene contentshould be minimized because it may be a polymerization catalyst poison.The isobutene may have been previously removed for other uses. Afterbeing used in the polymerization (during which much or most of the1-butene would have been polymerized), the butenes stream can bereturned to the refinery for further processing.

In many of the these polymerizations certain general trends may benoted, although for all of these trends there are exceptions. Thesetrends (and exceptions) can be gleaned from the Examples.

Pressure of the monomers (especially gaseous monomers such as ethylene)has an effect on the polymerizations in many instances. Higher pressureoften affects the polymer microstructure by reducing branching,especially in ethylene containing polymers. This effect is morepronounced for Ni catalysts than Pd catalysts. Under certain conditionshigher pressures also seem to give higher productivities and highermolecular weight. When an acrylate is present and a Pd catalyst is used,increasing pressure seems to decrease the acrylate content in theresulting copolymer.

Temperature also affects these polymerizations. Higher temperatureusually increases branching with Ni catalysts, but often has little sucheffect using Pd catalysts. With Ni catalysts, higher temperatures appearto often decrease molecular weight. With Pd catalysts, when acrylatesare present, increasing temperature usually increases the acrylatecontent of the polymer, but also often decreases the productivity andmolecular weight of the polymer.

Anions surprisingly also often affect molecular weight of the polymerformed. More highly coordinating anions often give lower molecularweight polymers. Although all of the anions useful herein are relativelyweakly coordinating, some are more strongly coordinating than others.The coordinating ability of such anions is known and has been discussedin the literature, see for instance W. Beck., et al., Chem. Rev., vol.88 p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p.927-942 (1993), both of which are hereby included by reference. Theresults found herein in which the molecular weight of the polymerproduced is related to the coordinating ability of the anion used, is inline with the coordinating abilities of these anions as described inBeck (p. 1411) and Strauss (p. 932, Table II).

In addition to the "traditional" weakly coordinating anions cited in theparagraph immediately above, heterogeneous anions may also be employed.In these cases, the true nature of the counterion is poorly defined orunknown. Included in this group are MAO, MMAO and related aluminoxaneswhich do not form true solutions. The resulting counterions are thoughtto bear anionic aluminate moieties related to those cited in theparagraph immediately above. Polymeric anionic materials such as Nafion"polyfluorosulfonic acid can function as non-coordinating counterions. Inaddition, a wide variety of heterogeneous inorganic materials can bemade to function as non-coordinating counterions. Examples would includealuminas, silicas, silica/aluminas, cordierites, clays, MgCl₂, and manyothers utilized as traditional supports for Ziegler-Natta olefinpolymerization catalysts. These are generally materials which have Lewisor Bronsted acidity. High surface area is usually desired and oftenthese materials will have been activated through some heating process.Heating may remove excess surface water and change the surface acidityfrom Bronsted to Lewis type. Materials which are not active in the rolemay often be made active by surface treatment. For instance, asurface-hydrated silica, zinc oxide or carbon can be treated with anorganoaluminum compound to provide the required functionality.

The catalysts described herein can be heterogenized through a variety ofmeans. The heterogeneous anions in the paragraph immediately above willall serve to heterogenize the catalysts. Catalysts can also beheterogenized by exposing them to small quantities of a monomer toencapsulate them in a polymeric material through which additionalmonomers will diffuse. Another method is to spray-dry the catalyst withits suitable non-coordinating counterion onto a polymeric support.Heterogeneous versions of the catalyst are particularly useful forrunning gas-phase polymerizations. The catalyst is suitably diluted anddispersed on the surface of the catalyst support to control the heat ofpolymerization. When applied to fluidized-bed polymerizations, theheterogeneous supports provide a convenient means of catalystintroduction.

Another item may effect the incorporation of polar monomers such asacrylic esters in olefin copolymers. It has been found that catalystscontaining less bulky α-diimines incorporate more of the polar monomerinto the polymer (one obtains a polymer with a higher percentage ofpolar monomer) than a catalyst containing a more bulky α-diimine,particularly when ethylene is the olefin comonomer. For instance, in anα-diimine of formula (VIII), if R² and R⁵ are 2,6-dimethylphenyl insteadof 2,6-diisopropylphenyl, more acrylic monomer will be incorporated intothe polymer. However, another common effect of using a less bulkycatalyst is to produce a polymer with lower molecular weight. Thereforeone may have to make a compromise between polar monomer content in thepolymer and polymer molecular weight.

When an olefinic carboxylic acid is polymerized into the polymer, thepolymer will of course contain carboxyl groups. Similarly in an estercontaining polymer, some or all of the ester groups may be hydrolyzed tocarboxyl groups (and vice versa). The carboxyl groups may be partiallyor completely converted into salts such as metallic salts. Suchpolymeric salts are termed ionomers. Ionomers are useful in adhesives,as ionomeric elastomers, and as molding resins. Salts may be made withions of metals such as Na, K, Zn, Mg, Al, etc. The polymeric salts maybe made by methods known to the artisan, for instance reaction of thecarboxylic acid containing polymers with various compounds of the metalssuch as bases (hydroxides, carbonates, etc.) or other compounds, such asacetylacetonates. Novel polymers that contain carboxylic acid groupsherein, also form novel ionomers when the carboxylic acid groups arepartially or fully converted to carboxylate salts.

When copolymers of an olefinic carboxylic acid or olefinic ester andselected olefins are made, they may be crosslinked by various methodsknown in the art, depending on the specific monomers used to make thepolymer. For instance, carboxyl or ester containing polymers may becrosslinked by reaction with diamines to form bisamides. Certainfunctional groups which may be present on the polymer may be induced toreact to crosslink the polymer. For instance epoxy groups (which may bepresent as glycidyl esters) may be crosslinked by reaction of the epoxygroups, see for instance Example 135.

It has also been found that certain fluorinated olefins, some of themcontaining other functional groups may be polymerized by nickel andpalladium catalysts. Note that these fluorinated olefins are includedwithin the definition of H₂ C═CHR¹⁷, wherein R¹⁷ can be considered to besubstituted hydrocarbyl, the substitution being fluorine and possiblyother substituents. Olefins which may be polymerized include H₂C═CH(CH₂)_(a) R_(f) R⁴² wherein a is an integer of 2 to 20, R_(f) isperfluoroalkylene optionally containing one or more ether groups, andR⁴² is fluorine or a functional group. Suitable functional groupsinclude hydrogen, chlorine, bromine or iodine, ester, sulfonic acid(--SO₃ H), and sulfonyl halide. Preferred groups for R⁴² includefluorine, ester, sulfonic acid, and sulfonyl fluoride. A sulfonic acidgroup containing monomer does not have to be polymerized directly. It ispreferably made by hydrolysis of a sulfonyl halide group already presentin an already made polymer. It is preferred that the perfluoroalkylenegroup contain 2 to 20 carbon atoms and preferred perfluoroalkylenegroups are --(CF₂)_(b) -- wherein b is 2 to 20, and --(CF₂)_(d) OCF₂ CF₂-- wherein d is 2 to 20. A preferred olefinic comonomer is ethylene or alinear α-olefin, and ethylene is especially preferred. Polymerizationsmay be carried out with many of the catalysts described herein, seeExamples 284 to 293.

As described herein, the resulting fluorinated polymers often don'tcontain the expected amount of branching, and/or the lengths of thebranches present are not those expected for a simple vinylpolymerization.

The resulting polymers may be useful for compatibilizing fluorinated andnonfluorinated polymers, for changing the surface characteristics offluorinated or nonfluorinated polymers (by being mixed with them), asmolding resins, etc. Those polymers containing functional groups may beuseful where those functional groups may react or be catalysts. Forinstance, if a polymer is made with a sulfonyl fluoride group (R⁴² issulfonyl fluoride) that group may be hydrolyzed to a sulfonic acid,which being highly fluorinated is well known to be a very strong acid.Thus the polymer may be used as an acid catalyst, for example for thepolymerization of cyclic ethers such as tetrahydrofuran.

In this use it has been found that this polymer is more effective than acompletely fluorinated sulfonic acid containing polymer. For such usesthe sulfonic acid content need not be high, say only 1 to 20 molepercent, preferably about 2 to 10 mole percent of the repeat units inthe polymer having sulfonic acid groups. The polymer may be crosslinked,in which case it may be soluble in the medium (for instancetetrahydrofuran), or it may be crosslinked so it swollen but notdissolved by the medium, Or it may be coated onto a substrate andoptionally chemically attached and/or crosslinked, so it may easily beseparated from the other process ingredients.

One of the monomers that may be polymerized by the above catalysts isethylene (E), either by itself to form a homopolymer, or with α-olefinsand/or olefinic esters or carboxylic acids. The structure of the polymermay be unique in terms of several measurable properties.

These polymers, and others herein, can have unique structures in termsof the branching in the polymer. Branching may be determined by NMRspectroscopy (see the Examples for details), and this analysis candetermine the total number of branches, and to some extent the length ofthe branches. Herein the amount of branching is expressed as the numberof branches per 1000 of the total methylene (--CH₂ --) groups in thepolymer, with one exception. Methylene groups that are in an estergrouping, i.e. --CO₂ R, are not counted as part of the 1000 methylenes.These methylene groups include those in the main chain and in thebranches. These polymers, which are E homopolymers, have a branchcontent of about 80 to about 150 branches per 1000 methylene groups,preferably about 100 to about 130 branches per 1000 methylene groups.These branches do not include polymer end groups. In addition thedistribution of the sizes (lengths) of the branches is unique. Of theabove total branches, for every 100 that are methyl, about 30 to about90 are ethyl, about 4 to about 20 are propyl, about 15 to about 50butyl, about 3 to about 15 are amyl, and about 30 to about 140 are hexylor longer, and it is preferred that for every 100 that are methyl, about50 to about 75 are ethyl, about 5 to about 15 are propyl, about 24 toabout 40 are butyl, about 5 to 10 are amyl, and about 65 to about 120are hexyl or larger. These E homopolymers are often amorphous, althoughin some there may be a small amount of crystallinity.

Another polyolefin, which is an E homopolymer that can be made by thesecatalysts has about 20 to about 150 branches per 1000 methylene groups,and, per 100 methyl groups, about 4 to about 20 ethyl groups, about 1 toabout 12 propyl groups, about 1 to about 12 butyl group, about 1 toabout 10 amyl groups, and 0 to about 20 hexyl or larger groups.Preferably this polymer has about 40 to about 100 methyl groups per 1000methylene groups, and per 100 methyl groups, about 6 to about 15 ethylgroups, about 2 to about 10 propyl groups, about 2 to about 10 butylgroups, about 2 to about 8 amyl groups, and about 2 to about 15 hexyl orlarger groups.

Many of the polyolefins herein, including homopolyethylenes, may becrosslinked by various methods known in the art, for instance by the useof peroxide or other radical generating species which can crosslinkthese polymers. Such crosslinked polymers are novel when theuncrosslinked polymers from which they are derived are novel, becausefor the most part the structural feature(s) of the uncrosslinkedpolymers which make them novel will be carried over into the crosslinkedforms.

In addition, some of the E homopolymers have an exceptionally lowdensity, less than about 0.86 g/mL, preferably about 0.85 g/mL or less,measured at 25° C. This density is based on solid polymer.

Homopolymers of polypropylene (P) can also have unusual structures.Similar effects have been observed with other α-olefins (e.g. 1-hexene).A "normal" P homopolymer will have one methyl group for each methylenegroup (or 1000 methyl groups per 1000 methylene groups), since thenormal repeat unit is --CH(CH₃)CH₂ --. However, using a catalyst offormula (I) in which M is Ni(II) in combination with an alkyl aluminumcompound it is possible to produce a P homopolymer with about 400 toabout 600 methyl groups per 1000 methylene groups, preferably about 450to about 550 methyl groups per 1000 methylene groups. Similar effectshave been observed with other α-olefins (e.g. 1-hexene).

In the polymerization processes described herein olefinic esters and/orcarboxylic acids may also be present, and of course become part of thecopolymer formed. These esters may be copolymerized with one or more ofE and one or more α-olefins. When copolymerized with E alone polymerswith unique structures may be formed.

In many such E/olefinic ester and/or carboxylic acid copolymers theoverall branching level and the distribution of branches of varioussizes are unusual. In addition, where and how the esters or carboxylicacids occur in the polymer is also unusual. A relatively high proportionof the repeat units derived from the olefinic esters are at the ends ofbranches. In such copolymers, it is preferred that the repeat unitsderived from the olefinic esters and carboxylic acids are about 0.1 to40 mole percent of the total repeat units, more preferably about 1 toabout 20 mole percent. In a preferred ester, m is 0 and R¹ ishydrocarbyl or substituted hydrocarbyl. It is preferred that R¹ is alkylcontaining 1 to 20 carbon atoms, more preferred that it contains 1 to 4carbon atoms, and especially preferred that R¹ is methyl.

One such preferred dipolymer has about 60 to 100 methyl groups(excluding methyl groups which are esters) per 1000 methylene groups inthe polymer, and contains, per 100 methyl branches, about 45 to about 65ethyl branches, about 1 to about 3 propyl branches, about 3 to about 10butyl branches, about 1 to about 3 amyl branches, and about 15 to about25 hexyl or longer branches. In addition, the ester and carboxylic acidcontaining repeat units are often distributed mostly at the ends of thebranches as follows. If the branches, and the carbon atom to which theyare attached to the main chain, are of the formula --CH(CH₂)_(n) CO₂ R¹,wherein the CH is part of the main chain, then in some of these polymersabout 40 to about 50 mole percent of ester groups are found in brancheswhere n is 5 or more, about 10 to about 20 mole percent when n is 4,about 20 to 30 mole percent when n is 1, 2 and 3 and about 5 to about 15mole percent when n is 0. When n is 0, an acrylate ester has polymerized"normally" as part of the main chain, with the repeat unit --CH₂ --CHCO₂R¹ --.

These branched polymers which contain olefin and olefinic ester monomerunits, particularly copolymers of ethylene and methyl acrylate and/orother acrylic esters are particularly useful as viscosity modifiers forlubricating oils, particularly automotive lubricating oils.

Under certain polymerization conditions, some of the polymerizationcatalysts described herein produce polymers whose structure is unusual,especially considering from what compounds (monomers) the polymers weremade, and the fact that polymerization catalysts used herein areso-called transition metal coordination catalysts (more than onecompound may be involved in the catalyst system, one of which mustinclude a transition metal). Some of these polymers were described in asomewhat different way above, and they may be described as "polyolefins"even though they may contain other monomer units which are not olefins(e.g., olefinic esters). In the polymerization of an unsaturatedcompound of the formula H₂ C═CH(CH₂)_(e) G, wherein e is 0 or an integerof 1 or more, and G is hydrogen or --CO₂ R¹, the usual ("normal")polymeric repeat unit obtained would be --CH₂ --CH (CH₂)_(e) G!--,wherein the branch has the formula --(CH₂)_(e) G. However, with some ofthe instant catalysts a polymeric unit may be --CH₂ --CH (CH₂)_(f) G!--,wherein f≠e, and f is 0 or an integer of 1 or more. If f<e, the "extra"methylene groups may be part of the main polymer chain. If f>e (partsof) additional monomer molecules may be incorporated into that branch.In other words, the structure of any polymeric unit may be irregular anddifferent for monomer molecules incorporated into the polymer, and thestructure of such a polymeric unit obtained could be rationalized as theresult of "migration of the active polymerizing site" up and down thepolymer chair, although this may not be the actual mechanism. This ishighly unusual, particularly for polymerizations employing transitionmetal coordination catalysts.

For "normal" polymerizations, wherein the polymeric unit --CH₂ --CH(CH₂)_(e) G!-- is obtained, the theoretical amount of branching, asmeasured by the number of branches per 1000 methylene (--CH₂ --) groupscan be calculated as follows which defines terms "theoretical branches"or "theoretical branching" herein: ##EQU1## In this equation, anα-olefin is any olefinic compound H₂ C═CH(CH₂)_(e) G wherein e≠0.Ethylene or an acrylic compound are the cases wherein e=0. Thus tocalculate the number of theoretical branches in a polymer made from 50mole percent ethylene (e=0), 30 mole percent propylene (e=1) and 20 molepercent methyl 5-heptenoate (e=4) would be as follows: ##EQU2## The"1000 methylenes" include all of the methylene groups in the polymer,including methylene groups in the branches.

For some of the polymerizations described herein, the actual amount ofbranching present in the polymer is considerably greater than or lessthan the above theoretical branching calculations would indicate. Forinstance, when an ethylene homopolymer is made, there should be nobranches, yet there are often many such branches. When an α-olefin ispolymerized, the branching level may be much lower or higher than thetheoretical branching level. It is preferred that the actual branchinglevel is at 90% or less of the theoretical branching level, morepreferably about 80% or less of the theoretical branching level, or 110%or more of the theoretical branching level, more preferably about 120%or more of the theoretical branching level. The polymer should also haveat least about 50 branches per 1000 methylene units, preferably about 75branches per 1000 methylene units, and more preferably about 100branches per 1000 methylene units. In cases where there are "0" branchestheoretically present, as in ethylene homopolymers or copolymers withacrylics, excess branches as a percentage cannot be calculated. In thatinstance if the polymer has 50 or more, preferably 75 or more branchesper 1000 methylene groups, it has excess branches (i.e. in branches inwhich f>0).

These polymers also have "at least two branches of different lengthscontaining less than 6 carbon atoms each." By this is meant thatbranches of at least two different lengths (i.e. number of carbonatoms), and containing less than 6 carbon atoms, are present in thepolymer. For instance the polymer may contain ethyl and butyl branches,or methyl and amyl branches.

As will be understood from the above discussion, the lengths of thebranches ("f") do not necessarily correspond to the original sizes ofthe monomers used ("e"). Indeed branch lengths are often present whichdo not correspond to the sizes of any of the monomers used and/or abranch length may be present "in excess". By "in excess" is meant thereare more branches of a particular length present than there weremonomers which corresponded to that branch length in the polymer. Forinstance, in the copolymerization of 75 mole percent ethylene and 25mole percent 1-butene it would be expected that there would be 125 ethylbranches per 1000 methylene carbon atoms. If there were more ethylbranches than that, they would be in excess compared to the theoreticalbranching. There may also be a deficit of specific length branches. Ifthere were less than 125 ethyl branches per 1000 methylene groups inthis polymer there would be a deficit. Preferred polymers have 90% orless or 110% or more of the theoretical amount of any branch lengthpresent in the polymer, and it is especially preferred if these branchesare about 80% or less or about 120% or more of the theoretical amount ofany branch length. In the case of the 75 mole percent ethylene/25 molepercent 1-butene polymer, the 90% would be about 113 ethyl branches orless, while the 110% would be about 138 ethyl branches or more. Suchpolymers may also or exclusively contain at least 50 branches per 1000methylene atoms with lengths which should not theoretically (asdescribed above) be present at all.

These polymers also have "at least two branches of different lengthscontaining less than 6 carbon atoms each." By this is meant thatbranches of at least two different lengths (i.e. number of carbonatoms), and containing less than 6 carbon atoms, are present in thepolymer. For instance the polymer may contain ethyl and butyl branches,or methyl and amyl branches.

Some of the polymers produced herein are novel because of unusualstructural features. Normally, in polymers of alpha-olefins of theformula CH₂ ═CH(CH₂)_(a) H wherein a is an integer of 2 or more made bycoordination polymerization, the most abundant, and often the only,branches present in such polymers have the structure --(CH₂)_(a) H. Someof the polymers produced herein are novel because methyl branchescomprise about 25% to about 75% of the total branches in the polymer.Such polymers are described in Examples 139, 162, 173 and 243-245. Someof the polymers produced herein are novel because in addition to havinga high percentage (25-75%) of methyl branches (of the total branchespresent), they also contain linear branches of the structure --(CH₂)_(n)H wherein n is an integer of six or greater. Such polymers are describedin Examples 139, 173 and 243-245. Some of the polymers produced hereinare novel because in addition to having a high percentage (25-75%) ofmethyl branches (of the total branches present), they also contain thestructure (XXVI), preferably in amounts greater than can be accountedfor by end groups, and more preferably greater than 0.5 (XXVI) groupsper thousand methyl groups in the polymer greater than can be accountedfor by end groups. ##STR72##

Normally, homo- and copolymers of one or more alpha-olefins of theformula CH₂ ═CH(CH₂)_(a) H wherein a is an integer of 2 or more containas part of the polymer backbone the structure (XXV) ##STR73## whereinR³⁵ and R³⁶ are alkyl groups. In most such polymers of alpha-olefins ofthis formula (especially those produced by coordination-typepolymerizations), both of R³⁵ and R³⁶ are --(CH₂)_(a) H. However, incertain of these polymers described herein, about 2 mole percent ormore, preferably about 5 mole percent or more and more preferably about50 mole percent or more of the total amount of (XXV) in said polymerconsists of the structure where one of R³⁵ and R³⁶ is a methyl group andthe other is an alkyl group containing two or more carbon atoms.Furthermore, in certain of these polymers described herein, structure(XXV) may occur in side chains as well as in the polymer backbone.Structure (XXV) can be detected by ¹³ C NMR. The signal for the carbonatom of the methylene group between the two methine carbons in (XXV)usually occurs in the ¹³ C NMR at 41.9 to 44.0 ppm when one of R³⁵ andR³⁶ is a methyl group and the other is an alkyl group containing two ormore carbon atoms, while when both R³⁵ and R³⁶ contain 2 or more carbonatoms, the signal for the methylene carbon atom occurs at 39.5 to 41.9ppm. Integration provides the relative amounts of these structurespresent in the polymer. If there are interfering signals from othercarbon atoms in these regions, they must be subtracted from the totalintegrals to give correct values for structure (XXV).

Normally, homo- and copolymers of one or more alpha-olefins of theformula CH₂ ═CH(CH₂)_(a) H wherein a is an integer of 2 or more(especially those made by coordination polymerization) contain as partof the polymer backbone structure (XXIV) wherein n is 0, 1, or 2. When nis 0, this structure is termed "head to head" polymerization. When n is1, this structure is termed "head to tail" polymerization. When n is 2,this structure is termed "tail to tail" polymerization. In most suchpolymers of alpha-olefins of this formula (especially those produced bycoordination-type polymerizations), both of R³⁷ and R³⁸ are --(CH₂)_(a)H. However some of the polymers of alpha-olefins of this formuladescribed herein are novel in that they also contain structure (XXIV)wherein n=a, R³⁷ is a methyl group, and R³⁸ is an alkyl group with 2 ormore carbon atoms. ##STR74##

Normally polyethylene made by coordination polymerization has a linearbackbone with either no branching, or small amounts of linear branches.Some of the polyethylenes described herein are unusual in that theycontain structure (XXVII) which has a methine carbon that is not part ofthe main polymer backbone. ##STR75##

Normally, polypropylene made by coordination polymerization has methylbranches and few if any branches of other sizes. Some of thepolypropylenes described herein are unusual in that they contain one orboth of the structures (XXVIII) and (XXIX). ##STR76##

As the artisan understands, in coordination polymerization alpha-olefinsof the formula CH₂ ═CH(CH₂)_(a) H may insert into the growing polymerchain in a 1,2 or 2,1 manner. Normally these insertion steps lead to1,2-enchainment or 2,1-enchainment of the monomer. Both of thesefundamental steps form a --(CH₂)_(a) H branch. However, with somecatalysts herein, some of the initial product of 1,2 insertion canrearrange by migration of the coordinated metal atom to the end of thelast inserted monomer before insertion of additional monomer occurs.This results in omega,2-enchainment and the formation of a methylbranch. ##STR77##

It is also known that with certain other catalysts, some of the initialproduct of 2,1 insertion can rearrange in a similar manner by migrationof the coordinated metal atom to the end of the last inserted monomer.This results in omega,1-enchainment and no branch is formed. ##STR78##

Of the four types of alpha-olefin enchainment, omega,1-enchainment isunique in that it does not generate a branch. In a polymer made from analpha-olefin of the formula CH₂ ═CH(CH₂)_(a) H, the total number ofbranches per 1000 methylene groups (B) can be expressed as:

    B=(1000) (1-X.sub.ω,1)/ (1-X.sub.ω,1)a+X.sub.ω,1 (a+2)!

where X.sub.ω,1 is the fraction of omega,1-enchainment

Solving this expression for X.sub.ω,1 gives:

    X.sub.ω,1 =(1000-aB)/(1000+2B)

This equation provides a means of calculating the fraction ofomega,1-enchainment in a polymer of a linear alpha-olefin from the totalbranching B. Total branching can be measured by ¹ H NMR or ¹³ C NMR.Similar equations can be written for branched alpha-olefins. Forexample, the equation for 4-methyl-1-pentene is:

    X.sub.ω,1 =(2000-2B)/(1000+2B)

Most polymers of alpha-olefins made by other coordination polymerizationmethods have less than 5% omega,1-enchainment. Some of the alpha-olefinpolymers described herein have unusually large amounts (say >5%) ofomega,1-enchainment. In essence this is similar to stating that apolymer made from an α-olefin has much less than the "expected" amountof branching. Although many of the polymerizations described herein givesubstantial amounts of ω,1- and other unusual forms of enchainment ofolefinic monomers, it has surprisingly been found that "unsymmetrical"α-diimine ligands of formula (VIII) give especially high amounts ofω,1-enchainment. In particular when R² and R⁵ are phenyl, and one orboth of these is substituted in such a way as different sized groups arepresent in the 2 and 6 position of the phenyl ring(s), ω,1-enchainmentis enhanced. For instance, if one or both of R² and R⁵ are2-t-butylphenyl, this enchainment is enhanced. In this context when R²and/or R⁵ are "substituted" phenyl the substitution may be not only inthe 2 and/or 6 positions, but on any other position in the phenyl ring.For instance, 2,5-di-t-butylphenyl, and 2-t-butyl-4,6-dichlorophenylwould be included in substituted phenyl.

The steric effect of various groupings has been quantified by aparameter called E_(s), see R. W. Taft, Jr., J. Am. Chem. Soc., vol. 74,p. 3120-3128, and M. S. Newman, Steric Effects in Organic Chemistry,John Wiley & Sons, New York, 1956, p. 598-603. For the purposes herein,the E_(s) values are those for o-substituted benzoates described inthese publications. If the value for E_(s) for any particular group isnot known, it can be determined by methods described in thesepublications. For the purposes herein, the value of hydrogen is definedto be the same as for methyl. It is preferred that difference in E_(s),when R² (and preferably also R⁵) is phenyl, between the groupssubstituted in the 2 and 6 positions of the phenyl ring is at least0.15, more preferably at least about 0.20, and especially preferablyabout 0.6 or more. These phenyl groups may be unsubstituted orsubstituted in any other manner in the 3, 4 or 5 positions.

These differences in E_(s) are preferred in a diimine such as (VIII),and in any of the polymerization processes herein wherein a metalcomplex containing an α-diimine ligand is used or formed. The synthesisand use of such α-diimines is illustrated in Examples 454-463.

Because of the relatively large amounts of ω,1-enchainment that may beobtained using some of the polymerization catalysts reported hereinnovel polymers can be made. Among these homopolypropylene (PP). In someof the PP's made herein the structure ##STR79## may be found. In thisstructure each C^(a) is a methine carbon atom that is a branch point,while each C^(b) is a methylene group that is more than 3 carbon atomsremoved from any branch point (C^(a)). Herein methylene groups of thetype --C^(b) H₂ -- are termed δ+ (or delta+) methylene groups. Methylenegroups of the type --C^(d) H₂ --, which are exactly the third carbonatom from a branch point, are termed γ (gamma) methylene groups. The NMRsignal for the δ+ methylene groups occurs at about 29.75 ppm, while theNMR signal for the γ methylene groups appears at about 30.15 ppm. Ratiosof these types of methylene groups to each other and the total number ofmethylene groups in the PP is done by the usual NMR integrationtechniques.

It is preferred that PP's made herein have about 25 to about 300 δ+methylene groups per 1000 methylene groups (total) in the PP.

It is also preferred that the ratio of δ+:γ methylene groups in the PPbe 0.7 to about 2.0.

The above ratios involving δ+ and γ methylene groups in PP are of coursedue to the fact that high relatively high ω,1 enchainment can beobtained. It is preferred that about 30 to 60 mole percent of themonomer units in PP be enchained in an ω,1 fashion. Using the aboveequation, the percent ω,1 enchainment for polypropylene can becalculated as:

    % ω,1=(100) (1000-B)/(1000+2B)

wherein B is the total branching (number of methyl groups) per 1000methylene groups in the polymer.

Homo- or copolymers of one or more linear α-olefins containing 3 to 8carbon atoms may also have δ+ carbon atoms in them, preferably at leastabout 1 or more δ+ carbon atoms per 1000 methylene groups.

The above polymerization processes can of course be used to makerelatively random copolymers (except for certain CO copolymers) ofvarious possible monomers. However, some of them can also be used tomake block polymers. A block polymer is conventionally defined as apolymer comprising molecules in which there is a linear arrangement ofblocks, a block being a portion of a polymer molecule which themonomeric units have at least one constitutional or configurationalfeature absent from adjacent portions (definition from H. Mark, et al.,Ed., Encyclopedia of Polymer Science and Engineering, Vol. 2, John Wiley& Sons, New York, 1985, p. 324). Herein in a block copolymer, theconstitutional difference is a difference in monomer units used to makethat block, while in a block homopolymer the same monomer(s) are usedbut the repeat units making up different blocks are different structureand/or ratios of types of structures.

Since it is believed that many of the polymerization processes hereinhave characteristics that often resemble those of livingpolymerizations, making block polymers may be relatively easy. Onemethod is to simply allow monomer(s) that are being polymerized to bedepleted to a low level, and then adding different monomer(s) or thesame combination of monomers in different ratios. This process may berepeated to obtain polymers with many blocks.

Lower temperatures, say about less than 0° C., preferably about -10° toabout -30° , tends to enhance the livingness of the polymerizations.Under these conditions narrow molecular weight distribution polymers maybe obtained (see Examples 367-369 and 371), and block copolymers mayalso be made (Example 370).

As pointed out above, certain polymerization conditions, such aspressure, affect the microstructure of many polymers. The microstructurein turn affects many polymer properties, such as crystallization. Thus,by changing polymerization conditions, such as the pressure, one canchange the microstructure of the part of the polymer made under thoseconditions. This of course leads to a block polymer, a polymer havedefined portions having structures different from other definedportions. This may be done with more than one monomer to obtain a blockcopolymer, or may be done with a single monomer or single mixture ofmonomers to obtain a block homopolymer. For instance, in thepolymerization of ethylene, high pressure sometimes leads to crystallinepolymers, while lower pressures give amorphous polymers. Changing thepressure repeatedly could lead to an ethylene homopolymer containingblocks of amorphous polyethylene and blocks of crystalline polyethylene.If the blocks were of the correct size, and there were enough of them, athermoplastic elastomeric homopolyethylene could be produced. Similarpolymers could possibly be made from other monomer(s), such aspropylene.

Homopolymers of α-olefins such as propylene, that is polymers which weremade from a monomer that consisted essentially of a single monomer suchas propylene, which are made herein, sometimes exhibit unusualproperties compared to their "normal" homopolymers. For instance, such ahomopolypropylene usually would have about 1000 methyl groups per 1000methylene groups. Polypropylenes made herein typically have about halfthat many methyl groups, and in addition have some longer chainbranches. Other α-olefins often give polymers whose microstructure isanalogous to these polypropylenes when the above catalysts are used forthe polymerization.

These polypropylenes often exhibit exceptionally low glass transitiontemperatures (Tg's). "Normal" polypropylene has a Tg of about -17° C.,but the polypropylenes herein have a Tg of -30° C. or less, preferablyabout -35° C. or less, and more preferably about -40° C. or less. TheseTg's are measured by Differential Scanning Calorimetry at a heating rateof 10° C./min, and the Tg is taken as the midpoint of the transition.These polypropylenes preferably have at least 50 branches (methylgroups) per 1000 carbon atoms, more preferably at least about 100branches per 1000 methylene groups.

Previously, when cyclopentene was coordination polymerized to highermolecular weights, the resulting polymer was essentially intractablebecause of its very high melting point, greatly above 300° C. Using thecatalysts here to homopolymerize cyclopentene results in a polymer thatis tractable, i.e., may be reformed, as by melt forming. Such polymershave an end of melting point of about 320° C. or less, preferably about300° C. or less, or a melting point of about 275° C. or less, preferablyabout 250° C. or less. The melting point is determined by DifferentialScanning Calorimetry at a heating rate of 15° C./min, and taking themaximum of the melting endotherm as the melting point. However thesepolymers tend to have relatively diffuse melting points, so it ispreferred to measure the "melting point" by the end of melting point.The method is the same, except the end of melting is taken as the end(high temperature end) of the melting endotherm which is taken as thepoint at which the DSC signal returns to the original (extrapolated)baseline. Such polymers have an average degree of polymerization(average number of cyclopentene repeat units per polymer chain) of about10 or more, preferably about 30 or more, and more preferably about 50 ormore.

In these polymers, enchainment of the cyclopentene repeat units isusually as cis-1,3-pentylene units, in contrast to many prior artcyclopentenes which were enchained as 1,2-cyclopentylene units. It ispreferred that about 90 mole percent or more, more preferably about 95mole percent or more of the enchained cyclopentene units be enchained as1,3-cyclopentylene units, which are preferably cis-1,3-cyclopentyleneunits.

The X-ray powder diffraction pattern of the instant poly(cyclopentenes)is also unique. To produce cyclopentene polymer samples of uniformthickness for X-ray measurements, powder samples were compressed intodisks approximately 1 mm thick and 32 mm in diameter. X-ray powderdiffraction patterns of the samples were collected over the range10°-50° 2θ. The diffraction data were collected using an automatedPhilips θ--θ diffractometer (Philips X'pert System) operating in thesymmetrical transmission mode (Ni-filtered CuKa radiation, equipped witha diffracted beam collimator (Philips Thin Film Collimator system), Xefilled proportional detector, fixed step mode (0.05°/step), 12.5sec./step, 1/4° divergence slit). Reflection positions were identifiedusing the peak finding routine in the APD suite of programs providedwith the X'pert System. The X-ray powder diffraction pattern hadreflections at approximately 17.3°, 19.3°, 24.2°, and 40.7° 2θ, whichcorrespond to d-spacings of approximately 0.512, 0.460, 0.368 and 0.222nm, respectively. These polymers have a monoclinic unit cell of theapproximate dimensions: a=0.561 nm; b=0.607 nm; c=7.37 nm; and g=123.2°.

Copolymers of cyclopentene and various other olefins may also be made.For instance a copolymer of ethylene and cyclopentene may also be made.In such a copolymer it is preferred that at least 50 mole percent, morepreferably at least about 70 mole percent, of the repeat units arederived from cyclopentene. As also noted above, many of thepolymerization systems described herein produce polyethylenes that haveconsiderable branching in them. Likewise the ethylene units which arecopolymerized with the cyclopentene herein may also be branched, so itis preferred that there be at least 20 branches per 1000 methylenecarbon atoms in such copolymers. In this instance, the "methylene carbonatoms" referred to in the previous sentence do not include methylenegroups in the cyclopentene rings. Rather it includes methylene groupsonly derived from ethylene or other olefin, but not cyclopentene.

Another copolymer that may be prepared is one from cyclopentene and anα-olefin, more preferably a linear αolefin. It is preferred in suchcopolymers that repeat units derived from cyclopentene are 50 molepercent or more of the repeat units. As mentioned above, α-olefins maybe enchained in a 1,ω fashion, and it is preferred that at least 10 molepercent of the repeat units derived from the α-olefin be enchained insuch a fashion. Ethylene may also be copolymerized with the cyclopenteneand α-olefin.

Poly(cyclopentene) and copolymers of cyclopentene, especially those thatare (semi)crystalline, may be used as molding and extrusion resins. Theymay contain various materials normally found in resins, such as fillers,reinforcing agents, antioxidants, antiozonants, pigments, tougheners,compatibilizers, dyes, flame retardant, and the like. These polymers mayalso be drawn or melt spun into fibers. Suitable tougheners andcompatibilizers include polycyclopentene resin which has been graftedwith maleic anhydride, an grafted EPDM rubber, a grafted EP rubber, afunctionalized styrene/butadiene rubber, or other rubber which has beenmodified to selectively bond to components of the two phases.

In all of the above homo- and copolymers of cyclopentene, whereappropriate, any of the preferred state may be combined any otherpreferred state(s).

The homo- and copolymers of cyclopentene described above may used ormade into certain forms as described below:

1. The cyclopentene polymers described above may be part of a polymerblend. That is they may be mixed in any proportion with one or moreother polymers which may be thermoplastics and/or elastomers. Suitablepolymers for blends are listed below in the listing for blends of otherpolymers described herein. One preferred type of polymer which may beblended is a toughening agent or compatibilizer, which is oftenelastomeric and/or contains functional groups which may helpcompatibilize the mixture, such as epoxy or carboxyl.

2. The polycyclopentenes described herein are useful in a nonwovenfabric comprising fibrillated three-dimensional network fibers preparedby using of a polycyclopentene resin as the principal component. It canbe made by flash-spinning a homogeneous solution containing apolycyclopentene. The resultant nonwoven fabric is excellent in heatresistance, dimensional stability and solvent resistance.

3. A shaped part of any of the cyclopentene containing resins. This partmay be formed by injection molding, extrusion, and thermoforming.Exemplary uses include molded part for automotive use, medical treatmentcontainer, microwave-range container, food package container such as hotpacking container, oven container, retort container, etc., andheat-resisting transparent container such as heat-resisting bottle.

4. A sheet or film of any of the cyclopentene containing resins. Thissheet or film may be clear and may be used for optical purposes (i.e.breakage resistant glazing). The sheet or film may be oriented orunoriented. Orientation may be carried out by any of the known methodssuch a uniaxial or biaxial drawing. The sheet or film may be stampableor thermoformable.

5. The polycyclopentene resins are useful in nonwoven fabrics ormicrofibers which are produced by melt-blowing a material containing asa main component a polycyclopentene. A melt-blowing process forproducing a fabric or fiber comprises supplying a polycyclopentene in amolten form from at least one orifice of a nozzle into a gas streamwhich attenuates the molten polymer into microfibers. The nonwovenfabrics are excellent in heat-resistant and chemical resistantcharacteristics, and are suitable for use as medical fabrics, industrialfilters, battery separators and so forth. The microfibers areparticularly useful in the field of high temperature filtration,coalescing and insulation.

6. A laminate in which one or more of the layers comprises acyclopentene resin. The laminate may also contain adhesives, and otherpolymers in some or all of the layers, or other materials such as paper,metal foil, etc. Some or all of the layers, may be oriented in the sameor different directions. The laminate as a whole may also be oriented.Such materials are useful for containers, or other uses where barrierproperties are required.

7. A fiber of a cyclopentene polymer. This fiber may be undrawn or drawnto further orient it. It is useful for apparel and in industrialapplication where heat resistance and/or chemical resistance areimportant.

8. A foam or foamed object of a cyclopentene polymer. The foam may beformed in any conventional manner such as by using blowing agents.

9. The cyclopentene resins may be microporous membranes. They may beused in process wherein semipermeable membranes are normally used.

In addition, the cyclopentene resins may be treated or mixed with othermaterials to improve certain properties, as follows:

1. They may further be irradiated with electron rays. This oftenimproves heat resistance and/or chemical resistance, and is relativelyinexpensive. Thus the molding is useful as a material required to havehigh heat resistance, such as a structural material, a food containermaterial, a food wrapping material or an electric or electronic partmaterial, particularly as an electric or electronic part material,because it is excellent in soldering resistance.

2. Parts with a crystallinity of at least 20% may be obtained bysubjecting cyclopentene polymers having an end of melting point between240° and 300° C. to heat treatment (annealing) at a temperature of 120°C. to just below the melting point of the polymer. Preferred conditionsare a temperature of 150° to 280° C. for a period of time of 20 secondsto 90 minutes, preferably to give a cyclopentene polymer which has aheat deformation temperature of from 200° to 260° C. These parts havegood physical properties such as heat resistance and chemicalresistance, and thus are useful for, for example, general constructionmaterials, electric or electronic devices, and car parts.

3. Cyclopentene resins may be nucleated to promote crystallizationduring processing. An example would be a polycyclopentene resincomposition containing as main components (A) 100 parts by weight of apolycyclopentene and (B) 0.01 to 25 parts by weight of one or morenucleating agents selected from the group consisting of (1) metal saltsof organic acids, (2) inorganic compounds, (3) organophosphoruscompounds, and/or (4) metal salts of ionic hydrocarbon copolymer.Suitable nucleating agents may be sodiummethylenebis(2,4-di-tertbutylphenyl) acid phosphate, sodiumbis(4-tert-butylphenyl) phosphate, aluminum p-(tert-butyl) benzoate,talc, mica, or related species. These could be used in a process forproducing polycyclopentene resin moldings by molding the abovepolycyclopentene resin composition at a temperature above their meltingpoint.

4. Flame retardants and flame retardant combinations may be added to acyclopentene polymer. Suitable flame retardants include a halogen-basedor phosphorus-based flame retardant, antimony trioxide, antimonypentoxide, sodium antimonate, metallic antimony, antimony trichloride,antimony pentachloride, antimony trisulfide, antimony pentasulfide, zincborate, barium metaborate or zirconium oxide. They may be used inconventional amounts.

5S. Antioxidants may be used in conventional amounts to improve thestability of the cyclopentene polymers. For instance 0.005 to 30 partsby weight, per 100 parts by weight of the cyclopentene polymer, of anantioxidant selected from the group consisting of a phosphorouscontaining antioxidant, a phenolic antioxidant or a combination thereof.The phosphorous containing antioxidant may be a monophosphite ordiphosphite or mixture thereof and the phenolic antioxidant may be adialkyl phenol, trialkyl phenol, diphenylmonoalkoxylphenol, a tetraalkylphenol, or a mixture thereof. A sulfur-containing antioxidant may alsobe used alone or in combination with other antioxidants.

6. Various fillers or reinforcers, such as particulate or fibrousmaterials, may be added to improve various physical properties.

7. "Special" physical properties can be obtained by the use of specifictypes of materials. Electrically conductive materials such as finemetallic wires or graphite may be used to render the polymerelectrically conductive. The temperature coefficient of expansion may beregulated by the use of appropriate fillers, and it may be possible toeven obtain materials with positive coefficients of expansion. Suchmaterials are particularly useful in electrical and electronic parts.

8. The polymer may be crosslinked by irradiation or chemically as byusing peroxides, optionally in the presence of suitable coagents.Suitable peroxides include benzoyl peroxide, lauroyl peroxide, dicumylperoxide, tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylcumylperoxide, tert-butylhydroperoxide,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,1,1-bis(tert-butylperoxyisopropyl)benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,n-butyl-4,4-bis(tert-butylperoxy)valerate,2,2-bis(tert-butylperoxy)butane and tert-butylperoxybenzene.

When polymerizing cyclopentene, it has been found that some of theimpurities that may be found in cyclopentene poison or otherwiseinterfere with the polymerizations described herein. Compounds such as1,3-pentadiene (which can be removed by passage through 5A molecularsieves), cyclopentadiene (which can be removed by distillation from Na),and methylenecyclobutane (which can be removed by distillation frompolyphosphoric acid), may interfere with the polymerization, and theirlevel should be kept as low as practically possible.

The above polymers (in general) are useful in many applications.Crystalline high molecular weight polymers are useful as molding resins,and for films for use in packaging. Amorphous resins are useful aselastomers, and may be crosslinked by known methods, such as by usingfree radicals. When such amorphous resins contain repeat units derivedfrom polar monomers they are oil resistant. Lower molecular weightpolymers are useful as oils, such as in polymer processing aids. Whenthey contain polar groups, particularly carboxyl groups, they are usefulin adhesives.

In many of the above polymerizations, the transition metal compoundsemployed as (part of the) catalysts contain(s) (a) metal atom(s) in apositive oxidation state. In addition, these complexes may have a squareplanar configuration about the metal, and the metal, particularly nickelor palladium, may have a d⁸ electronic configuration. Thus some of thesecatalysts may be said to have a metal atom which is cationic and has ad⁸ -square planar configuration.

In addition these catalysts may have a bidentate ligand whereincoordination to the transition metal is through two different nitrogenatoms or through a nitrogen atom and a phosphorus atom, these nitrogenand phosphorus atoms being part of the bidentate ligand. It is believedthat some of these compounds herein are effective polymerizationcatalysts at least partly because the bidentate ligands have sufficientsteric bulk on both sides of the coordination plane (of the squareplanar complex). Some of the Examples herein with the various catalystsof this type illustrate the degree of steric bulk which may be neededfor such catalysts. If such a complex contains a bidentate ligand whichhas the appropriate steric bulk, it is believed that it producespolyethylene with a degree of polymerization of at least about 10 ormore.

It is also believed that the polymerization catalysts herein areeffective because unpolymerized olefinic monomer can only slowlydisplace from the complex a coordinated olefin which may be formed byβ-hydride elimination from the growing polymer chain which is attachedto the transition metal. The displacement can occur by associativeexchange. Increasing the steric bulk of the ligand slows the rate ofassociative exchange and allows polymer chain growth. A quantitativemeasure of the steric bulk of the bidentate ligand can be obtained bymeasuring at -85° C. the rate of exchange of free ethylene withcomplexed ethylene in a complex of formula (XI) as shown in equation 1using standard ¹ H NMR techniques, which is called herein the EthyleneExchange Rate (EER). The neutral bidentate ligand is represented by YNwhere Y is either N or P. The EER is measured in this system. In thismeasurement system the metal is always Pd, the results being applicableto other metals as noted below. Herein it is preferred for catalysts tocontain bidentate ligands for which the second order rate constant forEthylene Exchange Rate is about 20,000 L-mol⁻¹ s⁻¹ or less when themetal used in the polymerization catalyst is palladium, more preferablyabout 10,000 L-mol⁻¹ s⁻¹ or less, and more preferably about 5,000L-mol⁻¹ s⁻¹ or less. When the metal in the polymerization catalyst isnickel, the second order rate constant (for the ligand in EERmeasurement) is about 50,000 L-mol⁻¹ s⁻¹, more preferably about 25,000L-mol⁻¹ s⁻¹ or less, and especially preferably about 10,000 L-mol⁻¹ s⁻¹or less. Herein the EER is measured using the compound (XI) in aprocedure (including temperature) described in Examples 21-23. ##STR80##In these polymerizations it is preferred if the bidentate ligand is anα-diimine. It is also preferred if the olefin has the formula R¹⁷CH═CH₂, wherein R¹⁷ is hydrogen or n-alkyl.

In general for the polymers described herein, blends may be preparedwith other polymers, and such other polymers may be elastomers,thermoplastics or thermosets. By elastomers are generally meant polymerswhose Tg (glass transition temperature) and Tm (melting point), ifpresent, are below ambient temperature, usually considered to be about20° C. Thermoplastics are those polymers whose Tg and/or Tm are at orabove ambient temperature. Blends can be made by any of the commontechniques known to the artisan, such as solution blending, or meltblending in a suitable apparatus such as a single or twin-screwextruder. Specific uses for the polymers of this application in theblends or as blends are listed below.

Blends may be made with almost any kind of elastomer, such as EP, EPDM,SBR, natural rubber, polyisoprene, polybutadiene, neoprene, butylrubber, styrene-butadiene block copolymers, segmentedpolyester-polyether copolymers, elastomeric polyurethanes, chlorinatedor chlorosulfonated polyethylene, (per)fluorinated elastomers such ascopolymers of vinylidene fluoride, hexafluoropropylene and optionallytetrafluoroethylene, copolymers of tezrafluoroethylene andperfluoro(methyl vinyl ether), and copolymers of tetrafluoroethylene andpropylene.

Suitable thermoplastics which are useful for blending with the polymersdescribed herein include: polyesters such as poly(ethyleneterephthalate), poly(butylene terephthalate), and poly(ethyleneadipate); polyamides such as nylon-6, nylon-6,6, nylon-12, nylon-12,12,nylon-11, and a copolymer of hexamethylene diamine, adipic acid andterephthalic acid; fluorinated polymers such as copolymers of ethyleneand vinylidene fluoride, copolymers of tetrafluoroethylene andhexafluoropropylene, copolymers of tetrafluoroethylene and aperfluoro(alkyl vinyl ether) such as perfluoro(propyl vinyl ether), andpoly(vinyl fluoride); other halogenated polymers such a poly(vinylchloride) and poly(vinylidene chloride) and its copolymers; polyolefinssuch as polyethylene, polypropylene and polystyrene, and copolymersthereof; (meth)acrylic polymers such a poly(methyl methacrylate) andcopolymers thereof; copolymers of olefins such as ethylene with various(meth) acrylic monomers such as alkyl acrylates, (meth)acrylic acid andionomers thereof, and glycidyl (meth)acrylate); aromatic polyesters suchas the copolymer of Bisphenol A and terephthalic and/or isophthalicacid; and liquid crystalline polymers such as aromatic polyesters oraromatic poly(ester-amides).

Suitable thermosets for blending with the polymers described hereininclude epoxy resins, phenol-formaldehyde resins, melamine resins, andunsaturated polyester resins (sometimes called thermoset polyesters).Blending with thermoset polymers will often be done before the thermosetis crosslinked, using standard techniques.

The polymers described herein may also be blended with uncrosslinkedpolymers which are not usually considered thermoplastics for variousreasons, for instance their viscosity is too high and/or their meltingpoint is so high the polymer decomposes below the melting temperature.Such polymers include poly(tetrafluoroethylene), aramids such aspoly(p-phenylene terephthalate) and poly(m-phenylene isophthalate),liquid crystalline polymer such as poly(benzoxazoles), and non-meltprocessible polyimides which are often aromatic polyimides.

All of the polymers disclosed herein may be mixed with various additivesnormally added to elastomers and thermoplastics see EPSE (below), vol.14, p. 327-410!. For instance reinforcing, non-reinforcing andconductive fillers, such as carbon black, glass fiber, minerals such asclay, mica and talc, glass spheres, barium sulfate, zinc oxide, carbonfiber, and aramid fiber or fibrids, may be used. Antioxidants,antiozonants, pigments, dyes, delusterants, compounds to promotecrosslinking may be added. Plasticizers such as various hydrocarbon oilsmay also be used.

The following listing is of some uses for polyolefins, which are madefrom linear olefins and do not include polar monomers such as acrylates,which are disclosed herein. In some cases a reference is given whichdiscusses such uses for polymers in general. All of these references arehereby included by reference. For the references, "U" refers to W.Gerhartz, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry,5th Ed. VCH Verlagsgesellschaft mBH, Weinheim, for which the volume andpage number are given, "ECT3" refers to the H. F. Mark, et al., Ed.,Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., John Wiley &Sons, New York, "ECT4" refers to the J. I Kroschwitz, et al., Ed.,Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., John Wiley &Sons, New York, for which the volume and page number are given, "EPST"refers to H. F. Mark, et al., Ed., Encyclopedia of Polymer Science andTechnology, 1st Ed., John Wiley & Sons, New York, for which the volumeand page number are given, "EPSE" refers to H. F. Mark, et al., Ed.,Encyclopedia of Polymer Science and Engineering, 2nd Ed., John Wiley &Sons, New York, for which volume and page numbers are given, and "PM"refers to J. A. Brydson, ed., Plastics Materials, 5 Ed.,Butterworth-Heinemann, Oxford, UK, 1989, and the page is given. In theseuses, a polyethylene, polypropylene and a copolymer of ethylene andpropylene are preferred.

1. Tackifiers for low strength adhesives (U, vol. A1, p. 235-236) are ause for these polymers. Elastomeric and/or relatively low molecularweight polymers are preferred.

2. An oil additive for smoke suppression in single-stroke gasolineengines is another use. Elastomeric polymers are preferred.

3. The polymers are useful as base resins for hot melt adhesives (U,vol. A1, p. 233-234), pressure sensitive adhesives (U, vol. A1, p.235-236) or solvent applied adhesives. Thermoplastics are preferred forhot melt adhesives. The polymers may also be used in a carpetinstallation adhesive.

4. Lubricating oil additives as Viscosity Index Improvers for multigradeengine oil (ECT3, Vol 14, p. 495-496) are another use. Branched polymersare preferred. Ethylene copolymer with acrylates or other polar monomerswill also function as Viscosity Index Improvers for multigrade engineoil with the additional advantage of providing some dispersancy.5.Polymer for coatings and/or penetrants for the protection of variousporous items such as lumber and masonry, particularly out-of-doors. Thepolymer may be in a suspension or emulsion, or may be dissolved in asolvent.

6. Base polymer for caulking of various kinds is another use. Anelastomer is preferred. Lower molecular weight polymers are often used.

7. The polymers may be grafted with various compounds particularly thosethat result in functional groups such as epoxy, carboxylic anhydride(for instance as with a free radically polymerized reaction with maleicanhydride) or carboxylic acid (EPSE, vol. 12, p. 445). Suchfunctionalized polymers are particularly useful as tougheners forvarious thermoplastics and thermosets when blended. When the polymersare elastomers, the functional groups which are grafted onto them may beused as curesites to crosslink the polymers. Maleic anhydride-graftedrandomly-branched polyolefins are useful as tougheners for a wide rangeof materials (nylon, PPO, PPO/styrene alloys, PET, PBT, POM, etc.); astie layers in multilayer constructs such as packaging barrier films; ashot melt, moisture-curable, and coextrudable adhesives; or as polymericplasticizers. The maleic andhydride-grafted materials may be postreacted with, for example; amines, to form other functional materials.Reaction with aminopropyl trimethoxysilane would allow formoisture-curable materials. Reactions with di- and tri-amines wouldallow for viscosity modifications.

8. The polymers, particularly elastomers, may be used for modifyingasphalt, to improve the physical properties of the asphalt and/or extendthe life of asphalt paving.

9. The polymers may be used as base resins for chlorination orchlorosulfonation for making the corresponding chlorinated orchlorosulfonated elastomers. The unchlorinated polymers need not beelastomers themselves.

10. Wire insulation and jacketing may be made from any of thepolyolefins (see EPSE, vol. 17, p. 828-842). In the case of elastomersit may be preferable to crosslink the polymer after the insulation orjacketing is formed, for example by free radicals.

11. The polymers, particularly the elastomers, may be used as toughenersfor other polyolefins such as polypropylene and polyethylene.

12. The base for synthetic lubricants (motor oils) may be the highlybranched polyolefins described herein (ECT3, vol. 14, p. 496-501).

13. The branched polyolefins herein can be used as drip suppressantswhen added to other polymers.

14. The branched polyolefins herein are especially useful in blown filmapplications because of their particular rheological properties (EPSE,vol. 7, p. 88-106). It is preferred that these polymers have somecrystallinity.

15. The polymer described herein can be used to blend with wax forcandles, where they would provide smoke suppression and/or drip control.

16. The polymers, especially the branched polymers, are useful as baseresins for carpet backing, especially for automobile carpeting.

17. The polymers, especially those which are relatively flexible, areuseful as capliner resins for carbonated and noncarbonated beverages.

18. The polymers, especially those having a relatively low meltingpoint, are useful as thermal transfer imaging resins (for instance forimaging tee-shirts or signs).

19. The polymers may be-used for extrusion or coextrusion coatings ontoplastics, metals, textiles or paper webs.

20. The polymers may be used as a laminating adhesive for glass.

21. The polymers are useful as for blown or cast films or as sheet (seeEPSE, vol. 7 p. 88-106; ECT4, vol. 11, p. 843-856; PM, p. 252 and p.432ff). The films may be single layer or multilayer, the multilayerfilms may include other polymers, adhesives, etc. For packaging thefilms may be stretch-wrap, shrink-wrap or cling wrap. The films areuseful form many applications such as packaging foods, geomembranes andpond liners. It is preferred that these polymers have somecrystallinity.

22. The polymers may be used to form flexible or rigid foamed objects,such as cores for various sports items such as surf boards and linersfor protective headgear. Structural foams may also be made. It ispreferred that the polymers have some crystallinity. The polymer of thefoams may be crosslinked.

23. In powdered form the polymers may be used to coat objects by usingplasma, flame spray or fluidized bed techniques.

24. Extruded films may be formed from these polymers, and these filmsmay be treated, for example drawn. Such extruded films are useful forpackaging of various sorts.

25. The polymers, especially those that are elastomeric, may be used invarious types of hoses, such as automotive heater hose.

26. The polymers, especially those that are branched, are useful as pourpoint depressants for fuels and oils.

27. These polymers may be flash spun to nonwoven fabrics, particularlyif they are crystalline (see EPSE vol. 10, p. 202-253) They may also beused to form spunbonded polyolefins (EPSE, vol. 6, p. 756-760). Thesefabrics are suitable as house wrap and geotextiles.

28. The highly branched, low viscosity polyolefins would be good as baseresins for master-batching of pigments, fillers, flame-retardants, andrelated additives for polyolefins. 29. The polymers may be grafted witha compound containing ethylenic unsaturation and a functional group suchas a carboxyl group or a derivative of a carboxyl group, such as ester,carboxylic anhydride of carboxylate salt. A minimum grafting level ofabout 0.01 weight percent of grafting agent based on the weight of thegrafted polymer is preferred. The grafted polymers are useful ascompatibilizers and/or tougheners. Suitable grafting agents includemaleic, acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonicand cinnamic acids, anhydrides, esters and their metal salts and fumaricacid and their esters, anhydrides (when appropriate) and metal salts.

Copolymers of linear olefins with 4-vinylcyclohexene and other dienesmay generally be used for all of the applications for which the linearolefins polymers(listed above) may be used. In addition they may besulfur cured, so they generally can be used for any use for which EPDMpolymers are used, assuming the olefin/4-vinylcyclohexene polymer iselastomeric.

Also described herein are novel copolymers of linear olefins withvarious polar monomers such as acrylic acid and acrylic esters. Uses forthese polymers are given below. Abbreviations for references describingthese uses in general with polymers are the same as listed above forpolymers made from linear olefins.

1. Tackifiers for low strength adhesives (U, vol. A1, p. 235-236) are ause for these polymers. Elastomeric and/or relatively low molecularweight polymers are preferred.

2. The polymers are useful as base resins for hot melt adhesives (U,vol. A1, p. 233-234), pressure sensitive adhesives (U, vol. A1, p.235-236) or solvent applied adhesives. Thermoplastics are preferred forhot melt adhesives. The polymers may also be used in a carpetinstallation adhesive.

3. Base polymer for caulking of various kinds is another use. Anelastomer is preferred. Lower molecular weight polymers are often used.

4. The polymers, particularly elastomers, may be used for modifyingasphalt, to improve the physical properties of the asphalt and/or extendthe life of asphalt paving, see U.S. Pat. No. 3,980,598.

5. Wire insulation and jacketing may be made from any of the polymers(see EPSE, vol. 17, p. 828-842). In the case of elastomers it may bepreferable to crosslink the polymer after the insulation or jacketing isformed, for example by free radicals.

6. The polymers, especially the branched polymers, are useful as baseresins for carpet backing, especially for automobile carpeting.

7. The polymers may be used for extrusion or coextrusion coatings ontoplastics, metals, textiles or paper webs.

8. The polymers may be used as a laminating adhesive for glass.

9. The polymers are useful as for blown or cast films or as sheet (seeEPSE, vol. 7 p. 88-106; ECT4, vol. 11, p. 843-856; PM, p. 252 and p.432ff). The films may be single layer or multilayer, the multilayerfilms may include other polymers, adhesives, etc. For packaging thefilms may be stretch-wrap, shrink-wrap or cling wrap. The films areuseful form many applications such as packaging foods, geomembranes andpond liners. It is preferred that these polymers have somecrystallinity.

10. The polymers may be used to form flexible or rigid foamed objects,such as cores for various sports items such as surf boards and linersfor protective headgear. Structural foams may also be made. It ispreferred that the polymers have some crystallinity. The polymer of thefoams may be crosslinked.

11. In powdered form the polymers may be used to coat objects by usingplasma, flame spray or fluidized bed techniques.

12. Extruded films may be formed from these polymers, and these filmsmay be treated, for example drawn. Such extruded films are useful forpackaging of various sorts.

13. The polymers, especially those that are elastomeric, may be used invarious types of hoses, such as automotive heater hose.

14. The polymers may be used as reactive diluents in automotivefinishes, and for this purpose it is preferred that they have arelatively low molecular weight and/or have some crystallinity.

15. The polymers can be converted to ionomers, which when the possesscrystallinity can be used as molding resins. Exemplary uses for theseionomeric molding resins are golf ball covers, perfume caps, sportinggoods, film packaging applications, as tougheners in other polymers, andusually extruded) detonator cords.

16. The functional groups on the polymers can be used to initiate thepolymerization of other types of monomers or to copolymerize with othertypes of monomers. If the polymers are elastomeric, they can act astoughening agents.

17. The polymers can act as compatibilizing agents between various otherpolymers.

18. The polymers can act as tougheners for various other polymers, suchas thermoplastics and thermosets, particularly if the olefin/polarmonomer polymers are elastomeric.

19. The polymers may act as internal plasticizers for other polymers inblends. A polymer which may be plasticized is poly(vinyl chloride).

20. The polymers can serve as adhesives between other polymers.

21. With the appropriate functional groups, the polymers may serve ascuring agents for other polymers with complimentary functional groups(i.e., the functional groups of the two polymers react with each other).

22. The polymers, especially those that are branched, are useful as pourpoint depressants for fuels and oils.

23. Lubricating oil additives as Viscosity Index Improvers formultigrade engine oil (ECT3, Vol 14, p. 495-496) are another use.Branched polymers are preferred. Ethylene copolymer with acrylates orother polar monomers will also function as Viscosity Index Improvers formultigrade engine oil with the additional advantage of providing somedispersancy.

24. The polymers may be used for roofing membranes.

25. The polymers may be used as additives to various molding resins suchas the so-called thermoplastic olefins to improve paint adhesion, as inautomotive uses.

Polymers with or without polar monomers present are useful in thefollowing uses. Preferred polymers with or without polar monomers arethose listed above in the uses for each "type".

1. A flexible pouch made from a single layer or multilayer film (asdescribed above) which may be used for packaging various liquid productssuch as milk, or powder such as hot chocolate mix. The pouch may be heatsealed. It may also have a barrier layer, such as a metal foil layer.

2. A wrap packaging film having differential cling is provided by a filmlaminate, comprising at least two layers; an outer reverse which is apolymer (or a blend thereof) described herein, which contains atackifier in sufficent amount to impart cling properties; and an outerobverse which has a density of at least about 0.916 g/mL which haslittle or no cling, provided that a density of the outer reverse layeris at least 0.008 g/mL less than that of the density of the outerobverse layer. It is preferred that the outer obverse layer is linearlow density polyethylene, and the polymer of the outer obverse layerhave a density of less than 0.90 g/mL. All densities are measured at 25°C.

3. Fine denier fibers and/or multifilaments. These may be melt spun.They may be in the form of a filament bundle, a non-woven web, a wovenfabric, a knitted fabric or staple fiber.

4. A composition comprising a mixture of the polymers herein and anantifogging agent. This composition is especially useful in film orsheet form because of its antifogging properties.

5. Elastic, randomly-branched olefin polymers are disclosed which havevery good processability, including processing indices (PI's) less thanor equal to 70 percent of those of a comparative linear olefin polymerand a critical shear rate at onset of surface melt fracture of at least50 percent greater than the critical shear rate at the onset of surfacemelt fracture of a traditional linear olefin polymer at about the sameI2 and Mw/Mn. The novel polymers may have higher low/zero shearviscosity and lower high shear viscosity than comparative linear olefinpolymers made by other means. These polymers may be characterized ashaving: a) a melt flow ratio, I10/I2,≧5.63, b) a molecular weightdistribution, Mw/Mn, defined by the equation: Mw/Mn≦(I10/I2)-4.63, andc) a critical shear rate at onset of surface melt fracture of at least50 percent greater than the critical shear rate at the onset of surfacemelt fracture of a linear olefin polymer having about the same I2 andMw/Mn. Some blends of these polymer are characterized as having: a) amelt flow ratio, I10/I2,≧5.63, b) a molecular weight distribution,Mw/Mn, defined by the equation: Mw/Mn≦(I10/I2)-4.63, and c) a criticalshear rate at onset of surface melt fracture of at least 50 percentgreater than the critical shear rate at the onset of surface meltfracture of a linear olefin polymer having about the same I2 and Mw/Mnand (b) at least one other natural or synthetic polymer chosen from thepolymer of claims 1, 3, 4, 6, 332, or 343, a conventional high densitypolyethylene, low density polyethylene or linear low densitypolyethylene polymer. The polymers may be further characterized ashaving a melt flow ratio, I10/I2,≧5.63, a molecular weight distribution,Mw/Mn, defined by the equation: Mw/Mn≦(I10/I2)-4.63, and a criticalshear stress at onset of gross melt fracture of greater than about 400kPa (4×10⁶ dyne/cm²) and their method of manufacture are disclosed. Therandomly-branched olefin polymers preferably have a molecular weightdistribution from about 1.5 to about 2.5. The polymers described hereinoften have improved processability over conventional olefin polymers andare useful in producing fabricated articles such as fibers, films, andmolded parts. For this paragraph, the value I2 is measured in accordancewith ASTM D-1238-190/2.16 and I10 is measured in accordance with ASTMD-1238-190/10; critical shear rate at onset of surface melt fracture andprocessing index (PI) are defined in U.S. Pat. No. 5,278,272, which ishereby included by reference.

In another process described herein, the product of the processdescribed herein is an α-olefin. It is preferred that in the process alinear α-olefin is produced. It is also preferred that the α-olefincontain 4 to 32, preferably 8 to 20, carbon atoms. ##STR81##

When,(XXXI) is used as a catalyst, a neutral Lewis acid or a cationicLewis or Bronsted acid whose counterion is a weakly coordinating anionis also present as part of the catalyst system (sometimes called a"first compound" in the claims). By a "neutral Lewis acid" is meant acompound which is a Lewis acid capable for abstracting X⁻ from (I) toform a weakly coordinating anion. The neutral Lewis acid is originallyuncharged (i.e., not ionic). Suitable neutral Lewis acids include SbF₅,Ar₃ B (wherein Ar is aryl), and BF₃. By a cationic Lewis acid is meant acation with a positive charge such as Ag⁺, H⁺, and Na⁺.

A preferred neutral Lewis acid is an alkyl aluminum compound, such as R⁹₃ Al, R⁹ ₂ AlCl, R⁹ AlCl₂, and "R⁹ AlO" (alkylaluminoxane), wherein R⁹is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbonatoms. Suitable alkyl aluminum compounds include methylaluminoxane, (C₂H₅)₂ AlCl, C₂ H₅ AlCl₂, and (CH₃)₂ CHCH₂ !₃ Al.

Relatively noncoordinating anions are known in the art, and thecoordinating ability of such anions is known and has been discussed inthe literature, see for instance W. Beck., et al., Chem. Rev., vol. 88p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942(1993), both of which are hereby included by reference. Among suchanions are those formed from the aluminum compounds in the immediatelypreceding paragraph and X⁻, including R⁹ ₃ AlX⁻, R⁹ ₂ AlClX⁻, R⁹ AlCl₂X⁻, and "R⁹ AlOX⁻ ". Other useful noncoordinating anions include BAF⁻{BAF=tetrakis 3,5-bis(trifluoromethyl)phenyllborate}, SbF₆ ⁻, PF₆ ⁻, andBF₄ ⁻, trifluoromethanesulfonate, p-toluenesulfonate, (R_(f) SO₂)₂ N⁻,and (C₆ F₅)₄ B⁻.

The temperature at which the process is carried out is about -100° C. toabout +200° C., preferably about 0° C. to about 150° C., more preferablyabout 25° C. to about 100° C. It is believed that at highertemperatures, lower molecular weight α-olefins are produced, all otherfactors being equal. The pressure at which the polymerization is carriedout is not critical, atmospheric pressure to about 275 MPa being asuitable range. It is also believed that increasing the pressureincreases the relative amount of α-olefin (as opposed to internalolefin) produced.

The process to make α-olefins may be run in a solvent (liquid), and thatis preferred. The solvent may in fact be the α-olefin produced. Such aprocess may be started by using a deliberately added solvent which isgradually displaced as the reaction proceeds. By solvent it is notnecessarily meant that any or all of the starting materials and/orproducts are soluble in the (liquid) solvent.

In (I) it is preferred that R³ and R⁴ are both hydrogen or methyl or R³and R⁴ taken together are ##STR82## It is also preferred that each of Qand S is independently chlorine or bromine, and it is more preferredthat both of Q and S in (XXXI) are chlorine or bromine.

In (XXXI) R² and R⁵ are hydrocarbyl or substituted hydrocarbyl. Whatthese groups are greatly determines whether the α-olefins of thisprocess are made, or whether higher polymeric materials, i.e., materialscontaining over 25 ethylene units, are coproduced or produced almostexclusively. If R² and R⁵ are highly sterically hindered about thenickel atom, the tendency is to produce higher polymeric material. Forinstance, when R² and R⁵ are both 2,6-diisopropylphenyl mostly higherpolymeric material is produced. However, when R² and R⁵ are both phenyl,mostly the α-olefins of this process are produced. Of course this willalso be influenced by other reaction conditions such as temperature andpressure, as noted above. Useful groups for R² and R⁵ are phenyl, andp-methylphenyl.

As is understood by the artisan, in oligomerization reactions ofethylene to produce α-olefins, usually a mixture of such α-olefins isobtained containing a series of such α-olefins differing from oneanother by two carbon atoms (an ethylene unit). The process forpreparing α-olefins described herein produces products with a highpercentage of terminal olefinic groups (as opposed to internal olefinicgroups). The product mixture also contains a relatively high percentageof molecules which are linear. Finally relatively high catalystefficiencies can be obtained.

The α-olefins described as being made herein may also be made bycontacting ethylene with one of the compounds ##STR83## wherein R², R³,R⁴, and R⁵ are as defined (and preferred) as described above (for thepreparation of α-olefins), and T¹ is hydrogen or n-alkyl containing upto 38 carbon atoms, Z is a neutral Lewis base wherein the donating atomis nitrogen, sulfur, or oxygen, provided that if the donating atom isnitrogen then the pKa of the conjugate acid of that compound (measuredin water) is less than about 6, U is n-alkyl containing up to 38 carbonatoms, and X is a noncoordinating anion (see above). The processconditions for making α-olefins using (III) or (XXXIV) are the same asfor using (XXXI) to make these compounds except a Lewis or Bronsted acidneed not be present. Note that the double line in (XXXIV) represents acoordinated ethylene molecule. (XXXIV) may be made from (II) by reactionof (III) with ethylene. In other words, (XXXIV) may be considered anactive intermediate in the formation of α-olefin from (III). Suitablegroups for Z include dialkyl ethers such as diethyl ether, and alkylnitrites such as acetonitrile.

In general, α-olefins can be made by this process using as a catalyst aNi II! complex of an α-diimine of formula (VIII), wherein the Ni II!complex is made by any of the methods which are described above, usingNi 0!, Ni I! or Ni II! precursors. All of the process conditions, andpreferred groups on (VIII), are the same as described above in theprocess for making α-olefins.

EXAMPLES

In the Examples, the following convention is used for naming α-diiminecomplexes of metals, and the α-diimine itself. The α-diimine isindicated by the letters "DAB". To the left of the "DAB" are the twogroups attached to the nitrogen atoms, herein usually called R² and R⁵.To the right of the "DAB" are the groups on the two carbon atoms of theα-diimine group, herein usually termed R³ and R⁴. To the right of allthis appears the metal, ligands attached to the metal (such as Q, S andT), and finally any anions (X), which when "free" anions are designatedby a superscript minus sign (i.e.,X⁻). Of course if there is a "free"anion present, the metal containing moiety is cationic. Abbreviationsfor these groups are as described in the Specification in the Note afterTable 1. Analogous abbreviations are used for α-diimines, etc.

In the Examples, the following abbreviations are used:

ΔH_(f) --heat of fusion

acac--acetylacetonate

Bu--butyl

t-BuA--t-butyl acrylate

DMA--Dynamic Mechanical Analysis

DME--1,2-dimethoxyethane

DSC--Differential Scanning Calorimetry

E--ethylene

EOC--end of chain

Et--ethyl

FC-75--perfluoro(n-butyltetrahydrofuran)

FOA--fluorinated octyl acrylate

GPC--gel permeation chromatography

MA--methyl acrylate

MAO--methylaluminoxane

Me--methyl

MeOH--methanol

MMAO--a modified methylaluminoxane in which about 25 mole percent of themethyl groups have been replaced by isobutyl groups

M-MAO--see MMAO

MMAO-3A--see MMAO

Mn--number average molecular weight

MVK--methyl vinyl ketone

Mw--weight average molecular weight

Mz--viscosity average molecular weight

PD or P/D--polydispersity, Mw/Mn

Ph--phenyl

PMAO--see MAO

PMMA--poly(methyl methacrylate)

Pr--propyl

PTFE--polytetrafluoroethylene

RI--refractive index

RT (or rt)--room temperature

TCE--1,1,2,2-tetrachloroethane

Tc--temperature of crystallization

Td--temperature of decomposition

Tg--glass transition temperature

TGA--Thermogravimetric Analysis

THF--tetrahydrofuran

Tm--melting temperature

TO--turnovers, the number of moles of monomer polymerized per g-atom ofmetal in the catalyst used

UV--ultraviolet

Unless otherwise noted, all pressures are gauge pressures.

In the Examples, the following procedure was used to quantitativelydetermine branching, and the distribution of branch sizes in thepolymers (but not necessarily the simple number of branches as measuredby total number of methyl groups per 1000 methylene groups). 100 MHz ¹³C NMR spectra were obtained on a Varian Unity 400 MHz spectrometer usinga 10 mmprobe on typically 15-20 wt % solutions of the polymers and 0.05MCr(acetylacetonate)₃ in 1,2,4-trichlorobenzene (TCE) unlocked at120°-140° C. using a 90 degree pulse of 12.5 to 18.5 μsec, a spectralwidth of 26 to 35 kHz, a relaxation delay of 5-9 s, anacquisition timeof 0.64 sec and gated decoupling. Samples were preheated for at least 15min before acquiring data. Data acquisition time was typically 12 hr.per sample. The T¹ values of the carbons were measured under theseconditions to be all less than 0.9 s. The longest T¹ measured was forthe Bu⁺, end of chain resonance at 14 ppm, which was 0.84 s.Occasionally about 16 vol. % benzene-d_(e) was added to the TCB and thesample was run locked. Some samples were run in chloroform-d1, CDCl₃--d1, (locked) at 30° C. under similar acquisition parameters. T¹ 'swere also measured in CDCl₃ at ambient temperature on a typical samplewith 0.05M Cr(acetylacetonate)₃ to be all less than 0.68 s. In rarecases when Cr(acetylacetonate)₃ was not used, a 30-40 s recycle delaywas used to insure quantitation. The glycidyl acrylate copolymer was runat 100° C. with Cr(acetylacetonate)₃. Spectra are referenced to thesolvent--either the TCB highfield resonance at 127.8 ppm or thechloroform-d1 triplet at 77 ppm. A DEPT 135 spectrum was done on mostsamples to distinguish methyls and methines from methylenes. Methylswere distinguished from methines by chemical shift. EOC is end-of-chain.Assignments reference to following naming scheme:

1. xBy: By is a branch of length y carbons; x is the carbon beingdiscussed, the methyl at the end of the branch is numbered 1. Thus thesecond carbon from the end of a butyl branch is 2B4. Branches of lengthy or greater are designated as y⁺.

2. xEBy: EB is an ester ended-branch containing y methylenes. x is thecarbon being discussed, the first methylene adjacent to the estercarbonylis labeled 1. Thus the second methylene from the end of a 5methylene esterterminated branch would be 2EB5. ¹³ C NMR of modelcompounds for EBy type branches for y=0 and y=5⁺ confirm the peakpositions and assignments of these branches. In addition, a modelcompound for an EB1 branch is consistent with 2 dimensional NMR datausing the well know 2D NMR techniques of hsqc, hmbc, and hsqc-tocsy; the2D data confirms the presence of the EB5⁺, EB0, EB1 and otherintermediate length EB branches

3. The methylenes in the backbone are denoted with Greek letters whichdetermine how far from a branch point methine each methylene is. Thus ββ(beta beta) B denotes the central methylene in the following PCHRCH₂ CH₂CH₂ CHRP. Methylenes that are three or more carbons from a branch pointare designated as γ⁺ (gamma⁺).

4. When x in xBy or xEBy is replaced by a M, the methine carbon of thatbranch is denoted.

Integrals of unique carbons in each branch were measured and werereported as number of branches per 1000 methylenes (including methylenesin the backbone and branches). These integrals are accurate to ±5%relative for abundant branches and ±10 or 20% relative for branchespresent at less than 10 per 1000 methylenes.

Such types of analyses are generally known, see for instance "AQuantitative Analysis of Low Density (Branched) Polyethylenes byCarbon-13Fourier Transform Nuclear Magnetic Resonance at 67.9 MHz", D.E. Axelson, et al., Macromolecules 12 (1979) pp. 41-52; "Fine BranchingStructure in High-Pressure, Low Density Polyethylenes by 50.10-MHz 13CNMR Analysis", T. Usami et al., Macromolecules 17 (1984) pp. 1757-1761;and "Quantification of Branching in Polyethylene by 13C NMR UsingParamagneticRelaxation Agents", J. V. Prasad, et al., Eur. Polym. J. 27(1991) pp. 251-254 (Note that this latter paper is believed to have somesignificant typographical errors in it).

It is believed that in many of the polymers described herein which haveunusual branching, i.e., they have more or fewer branches than would beexpected for "normal" coordination polymerizations, or the distributionofsizes of the branches is different from that expected, that "brancheson branches" are also present. By this is meant that a branch from themain chain on the polymer may itself contain one or more branches. It isalso noted that the concept of a "main chain" may be a somewhat semanticargument if there are sufficient branches on branches in any particularpolymer.

By a polymer hydrocarbyl branch is meant a methyl group to a methine orquaternary carbon atom or a group of consecutive methylenes terminatedat one end by a methyl group and connected at the other end to a methineor quaternary carbon atom. The length of the branch is defined as thenumber of carbons from and including the methyl group to the nearestmethine or quaternary carbon atom, but not including the methine orquaternary carbonatom. If the number of consecutive methylene groups is"n" then the branch contains (or the branch length is) n+1. Thus thestructure (which represents part of a polymer)--CH₂ CH₂ CH CH₂ CH₂ CH₂CH₂ CH(CH₃)CH₂ CH₃ !CH₂ CH₂ CH₂ CH₂ -- contains 2 branches, a methyl andan ethyl branch.

For ester ended branches a similar definition is used. An ester branchrefers to a group of consecutive methylene groups terminated at one endbyan ester--COOR group, and connected at the other end to a methine orquaternary carbon atom. The length of the branch is defined as thenumber of consecutive methylene groups from the ester group to thenearest methine or quaternary carbon atom, but not including the methineor quaternary carbon atom. If the number of methylene groups is "n",then thelength of the branch is n. Thus --CH₂ CH₂ CH CH₂ CH₂ CH₂ CH₂CH(CH₃)CH₂ COOR!CH₂ CH₂ CH₂ CH₂ -- contains 2 branches, a methyl and ann=1 ester branch.

The ¹³ C NMR peaks for copolymers of cyclopentene and ethylene aredescribed based on the labeling scheme and assignments of A. Jerschow etal, Macromolecules 1995, 28, 7095-7099. The triads and pentads aredescribed as 1-cme, 1,3-ccmcc, 1,3-cmc, 2-cme, 2-cmc, 1,3-eme, 3-cme,and 4,5-cmc, where e=ethylene, c=cyclopentene, and m=meta cyclopentene(i.e. 1,3 enchainment). The same labeling is used forcyclopentene/1-pentene copolymer substituting p=pentene for e. Thesynthesis of diimines is reported in the literature (Tom Dieck, H.;Svoboda, M.; Grieser, T. Z. Naturforsch 1981, 36b, 823-832. Kliegman, J.M.; Barnes, R. K. J. Org. Chem. 1970, 35, 3140-3143.)

Example 1 (2, 6-i-PrPh)₂ DABMe₂ !PdMeCl

Et₂ O (75 mL) was added to a Schlenk flask containing CODPdMeCl(COD=1,5-cyclooctadiene) (3.53 g, 13.3 mmol) and a slight excess of(2,6-i-PrPh)₂ DABMe₂ (5.43 g, 13.4 mmol, 1.01 equiv). An orangeprecipitate began to form immediately upon mixing. The reaction mixturewas stirred overnight and the Et₂ O and free COD were then removed viafiltration. The product was washed with an additional 25 mL of Et₂ O andthen dried overnight in vacuo. A pale orange powder (7.18 g, 95.8%) wasisolated: ¹ H NMR (CD₂ Cl₂, 400 MHz) δ7.4-7.2 (m, 6, H_(aryl)), 3.06(septet, 2, J=6.81, CHMe₂), 3.01 (septet, 2, J=6.89, C'HMe₂), 2.04 and2.03 (N═C(Me)--C'(Me)═N), 1.40 (d, 6, J=6.79, C'HMeMe'), 1.36 (d, 6,J=6.76, CHMeMe'), 1.19 (d, 6, J=6.83, CHMeMe'), 1.18 (d, 6, J=6.87,C'HMeMe'), 0.36 (s, 3, PdMe); ¹³ C NMR (CD₂ Cl₂, 400 MHz) δ175.0 and170.3 (N═C--C'═N), 142.3 and 142.1 (Ar, Ar': C_(ipso)), 138.9 and 138.4(Ar, Ar': C_(O)), 128.0 and 127.1 (Ar, Ar':C_(p)), 124.3 and 123.5 (Ar,Ar': C_(m)), 29.3 (CHMe₂), 28.8 (C'HMe₂), 23.9, 23.8, 23.5 and 23.3(CHMeMe', C'HMeMe'), 21.5 and 20.1 (N═C(Me)--C'(Me)═N), 5.0 (J_(CH)=135.0, PdMe).

Example 2 (2,6-i-PrPh)₂ DABH₂ !PdMeCl

Following the procedure of Example 1, an orange powder was isolated in97.1% yield: ¹ H NMR (CD₂ Cl₂, 400 MHz) δ8.31 and 8.15 (s, 1 each,N═C(H)--C'(H)═N), 7.3-7.1 (m, 6, H_(aryl)), 3.22 (septet, 2, J=6.80,CHMe₂), 3.21 (septet, 2, J=6.86, C'HMe₂), 1.362, 1.356, 1.183 and 1.178(d, 6 each, J=7.75-6.90; CHMeMe', C'HMeMe'), 0.67 (s, 3, PdMe); ¹³ C NMR(CD₂ Cl₂, 100 MHz) δ164.5 (J_(CH) =179.0, N═C(H)), 160.6 (J_(CH) =178.0,N═C'(H)), 144.8 and 143.8 (Ar, Ar': C_(ipso)), 140.0 and 139.2 (Ar, Ar':C_(o)), 128.6 and 127.7 (Ar, Ar': C_(p)), 124.0 and 123.4 (Ar, Ar':C_(m)), 29.1 (CHMe₂) 28.6 (C'HMe₂), 24.7, 24.1, 23.1 and 22.7 (CHMeMe',C'HMeMe'), 3.0 (J_(CH) =134.0, PdMe). Anal. Calcd for (C₂₇ H₃₉ ClN₂ Pd):C, 60.79; H, 7.37; N, 5.25. Found: C, 60.63; H. 7.24; N, 5.25.

Example 3 (2, 6-MePh)₂ DABMe₂ !PdMeCl

Following the procedure of Example 1, a yellow powder was isolated in90.6%yield: ¹ H NMR (CD₂ Cl₂, 400 MHz) δ7.3-6.9 (m, 6, H_(aryl)), 2.22(s, 6, Ar, Ar': Me), 2.00 and 1.97 (N═C(Me)--C'(Me)═N), 0.25 (s, 3,PdMe).

Example 4 (2,6-MePh)₂ DABMe₂ !PdMeCl

Following the procedure of Example 1, an orange powder was isolated in99.0% yield: ¹ H NMR (CD₂ Cl₂, 400 MHz, 41° C.) δ8.29 and 8.14(N═C(H)--C'(H)═N), 7.2-7.1 (m, 6, H_(aryl)), 2.33 and 2.30 (s, 6 each,Ar, Ar': Me), 0.61 (s, 3, PdMe); ¹³ C NMR (CD₂ Cl₂, 100 MHz, 41° C.)δ165.1 (J_(CH) =179.2, N═C(H)), 161.0 (J_(CH) =177.8 (N═C'(H)), 147.3and146.6 (Ar, Ar': C_(ipso)) 129.5 and 128.8 (Ar, Ar': C_(o)), 128.8 and128.5 (Ar, Ar': C_(m)), 127.9 and 127.3 (Ar, Ar': C_(p)), 18.7 and18.2(Ar, Ar': Me), 2.07 (J_(CH) =136.4, PdMe)

Example 5 4-MePh)₂ DABMe₂ !PdMeCl

Following the procedure of Example 1, a yellow powder was isolated in92.1%yield: ¹ H NMR (CD₂ Cl₂, 400 Hz) δ7.29 (d, 2, J=8.55, Ar: H_(m)),7.26 (d, 2, J=7.83, Ar': H_(m)), 6.90 (d, 2, J=8.24, Ar': H_(o)), 6.83(d, 2, J=8.34, Ar: H_(o)), 2.39 (s, 6, Ar, Ar': Me), 2.15and 2.05 (s, 3each, N═C(Me)--C'(Me)═N), 0.44 (s, 3, PdMe); ¹³C NMR (CD₂ Cl₂, 100 MHz)δ176.0 and 169.9 (N═C--C'═N), 144.9 and 143.7 (Ar, Ar': C_(ipso)), 137.0and 136.9 (Ar, Ar': C_(p)), 130.0 and 129.3 (Ar, Ar': C_(m)), 122.0 and121.5 (Ar, Ar': C_(o)), 21.2 (N═C(Me)), 20.1 (Ar, Ar': Me), 19.8(N═C'(Me)), 2.21 (J_(CH) =135.3, PdMe). Anal. Calcd for (C₁₉ H₂₃ ClN₂Pd): C, 54.17; H, 5.50; N, 6.65. Found: C, 54.41; H, 5.37; N, 6.69.

Example 6 (4-MePh)₂ DABH₂ !PdMeCl

Following the procedure of Example 1, a burnt orange powder was isolatedin90.5% yield: Anal. Calcd for (C₁₇ H₁₉ ClN₂ Pd): C, 51.93; H,4.87; N,7.12. Found: C, 51.36; H, 4.80; N, 6.82.

Example 7 <{ (2,6-i-PrPh)₂ DABMe₂ !PdMe}₂ (μ-Cl))BAF⁻

Et₂ O (25 mL) was added to a mixture of (2,6-i-PrPh)₂ DABMe₂ !PdMeCl(0.81 g, 1.45 mmol) and 0.5 equiv of NaBAF (0.64 g, 0.73 mmol) at roomtemperature. A golden yellow solution and NaCl precipitate formedimmediately upon mixing. The reaction mixture was stirred overnight andthen filtered. After the Et₂ O was removed in vacuo, the product waswashed with 25 mL of hexane. The yellow powder was then dissolved in 25mL of CH₂ Cl₂ and the resulting solution was filtered in order toremoved traces of unreacted NaBAF. Removal of CH₂ Cl₂ in vacuo yielded agolden yellow powder (1.25 g, 88.2%): ¹ H NMR (CD₂ Cl₂, 400 MHz) δ7.73(s, 8, BAF: H_(o)), 7.57 (s, 4, BAF: H_(p)), 7.33 (t, 2, J=7.57, Ar:H_(p)), 7.27 (d, 4, J=7.69, Ar: H_(o)), 7.18 (t, 2, J=7.64, Ar: H_(p)),7.10 (d, 4, J=7.44, Ar': H_(o)), 2.88 (septet, 4, J=6.80, CHMe₂), 2.75(septet, 4, J=6.82, C'HMe₂), 2.05 and 2.00 (s, 6 each,N═C(Me)--C'(Me)═N), 1.22, 1.13, 1.08 and 1.01 (d, 12 each, J=6.61-6.99,CHMeMe', C'HMeMe'), 0.41 (s, 6, PdMe); ¹³ C NMR (CD₂ Cl₂, 100 MHz)δ177.1 and 171.2 (N═C--C'═N), 162.2 (q, J_(BC) =49.8, BAF: C_(ipso)),141.4 and 141.0 (Ar, Ar': C_(ipso)), 138.8 and 138.1 (Ar, Ar': C_(o)),135.2 (BAF: C_(p)) 129.3 (q, J_(CF) =31.6, BAF: C_(m)), 128.6 and 127.8(Ar, Ar': C_(p)), 125.0 (q, J_(CF) =272.5, BAF: CF₃), 124.5 and 123.8(Ar, Ar': C_(m))), 117.9 (BAF: C_(p)), 29.3 (CHMe₂), 29.0 (C'HMe₂),23.8, 23.7, 23.6 and 23.0 (CHMeMe', C'HMeMe'), 21.5 and 20.0(N═C(Me)--C'(Me)═N), 9.8 (J_(CH) =136.0, PdMe). Anal. Calcdfor (C₉₀ H₉₈BClF₂₄ N₄ Pd₂): C, 55.41; H, 5.06; N,2.87. Found: C, 55.83; H, 5.09; N,2.63.

Example 8 <{ (2,6-i-PrPh)₂ DABH₂ !PdMe}₂ (μ-Cl))BAF⁻

The procedure of Example 7 was followed with one exception, the removalof CH₂ Cl₂ in vacuo yielded a product that was partially an oil.Dissolving the compound in Et2O and then removing the Et₂ O in vacuoyielded a microcrystalline red solid (85.5%): ¹ H NMR (CD₂ Cl₂, 400 MHz)δ8.20 and 8.09 (s, 2 each, N═C(H)--C'(H)═N), 7.73 (s, 8, BAF: H_(o)),7.57 (s, 4, BAF: H_(p)), 7.37 (t, 2, J=7.73, Ar: H_(p)), 7.28 (d, 4,J=7.44, Ar: H_(m)), 7.24 (t, 2, Ar': H_(p)), 7.16 (d, 4, J=7.19, Ar':H_(m)), 3.04 (septet, 4, J=6.80, CHMe₂), 2.93 (septet, 4, J=6.80,C'HMe₂), 1.26 (d, 12, J=6.79, CHMeMe'), 1.14 (d, 12, J=6.83, CHMeMe'),1.11 (d, 12, J=6.80, C'HMeMe'), 1.06 (d, 12, J=6.79, C'HMeMe'), 0.74 (s,6, PdMe); ¹³ C NMR (CD₂ Cl₂, 100 MHz) δ166.0(J_(CH) =180.4, N═C(H)),161.9 (q, J_(BC) =49.6, BAF: C_(ipso)), 160.8 (J_(CH) =179.9, N═C'(H)),143.5 and 143.0 (Ar, Ar': C_(ipso)) 139.8 and 138.9 (Ar, Ar': C_(o)),135.2 (BAF: C_(o)), 129.3 (q, J_(CF) =31.4, BAF: C_(m)), 129.3 and 128.5(Ar, Ar': C_(p)), 125.0 (q, J_(CF) =272.4, BAF: CF₃), 124.3 and 123.7(Ar, Ar': C_(m)), 117.9 (BAF: C_(p)), 29.2 and 28.9 (CHMe₂, C'HMe₂),24.5, 24.1, 23.0, and 22.5 (CHMeMe', C'HMeMe'), 10.3 (PdMe).Anal. Calcdfor (C₈₆ H₉₀ BClF₂₄ N₄ Pd₂): C, 54.52;H, 4.97; N. 2.₉₆. Found: C, 54.97;H. 4.72; N. 2.71.

Example 9

Alternatively, the products of Examples 7 and 8 have been synthesized bystirring a 1:1 mixture of the appropriate PdMeCl compound and NaBAF inEt₂ O for ˜1 h. Removal of solvent yields the dimer +0.5 equiv of Na⁺(OEt₂)₂ BAF⁻. Washing the product mixture withhexane yields ether-freeNaBAF, which is insoluble in CH₂ Cl₂. Addition of CH₂ Cl₂ to the productmixture and filtration of thesolution yields salt-free dimer: ¹ H NMRspectral data are identical with that reported above.

For a synthesis of CODPdMe₂, see: Rudler-Chauvin, M., and Rudler, H. J.Organomet. Chem. 1977, 134, 115-119.

Example 10 (2,6-i-PrPh)₂ DABMe₂ !PdMe₂

A Schlenk flask containing a mixture of (2,6-i-PrPh)₂ DADMe₂ !PdMeCl(2.00 g, 3.57 mmol) and 0.5 equiv of Me₂ Mg (97.2 mg, 1.79 mmol) wascooled to -78° C., and the reaction mixture was then suspended in 165 mLof Et₂ O. The reaction mixture was allowed to warm to room temperatureand then stirred for 2 h, and the resulting brownsolution was thenfiltered twice. Cooling the solution to -30° C. yielded brown singlecrystals (474.9 mg, 24.6%, 2 crops): ¹ H NMR (C₆ D₆, 400 MHz) δ7.2-7.1(m, 6, H_(aryl)), 3.17 (septet, 4, J=6.92, CHMe₂), 1.39 (d, 12, J=6.74,CHMeMe'), 1.20 (N═C(Me)--C(Me)═N), 1.03 (d, 12, J=6.89, CHMeMe'), 0.51(s, 6, PdMe); ¹³ C NMR (C₆ D₆, 100 MHz) δ168.4 (N═C--C═N), 143.4 (Ar:C_(ipso)), 138.0 (Ar: C_(o)), 126.5 (Ar: C_(p)), 123.6 (Ar: C_(m)), 28.8(CHMe₂), 23.6 and 23.5 (CHMeMe'), 19.5 (N═C(Me)--C(Me)═N), -4.9 (J_(CH)=127.9, PdMe). Anal. Calcd for (C₃₀ H₄₆ N₂ Pd): C, 66.59; H, 8.57; N,5.18. Found: C, 66.77; H, 8.62; N, 4.91.

Example 11 (2,6-i-PrPh)₂ DABH₂ !PdMe₂

The synthesis of this compound in a manner analogous to Example 10,using 3.77 mmol of ArN═C(H)--C(H)═NAr and 1.93 mmol of Me₂ Mg yielded722.2 mg (37.4%) of a deep brown microcrystalline powder uponrecrystallization of the product from a hexane/toluene solvent mixture.

This compound was also synthesized by the following method: A mixture ofPd(acac)₂ (2.66 g, 8.72 mmol) and corresponding diimine (3.35 g,8.90mmol) was suspended in 100 mL of Et₂ O, stirred for 0.5 h at roomtemperature, and then cooled to -78° C. A solution of Me₂ Mg (0.499 g,9.18 mmol) in 50 mL of Et₂ O was then added via cannula to the coldreaction mixture. After stirring for 10 min at -78° C., the yellowsuspension was allowed to warm to room temperature and stirred for anadditional hour. A second equivalent of the diimine was then added tothe reaction mixture and stirring was continued for ˜4 days. The brownEt₂ O solution was then filtered and the solvent was removed invacuo toyield a yellow-brown foam. The product was then extracted with 75 mL ofhexane, and the resulting solution was filtered twice, concentrated,andcooled to -30° C. overnight to yield 1.43 g (32.0%) of brown powder: ¹ HNMR (C₆ D₆, 400 MHz) δ7.40 (s, 2, N═C(H)--C(H)═N), 7.12 (s, 6,H_(aryl)), 3.39 (septet, 4, J=6.86,CHMe₂), 1.30 (d, 12, J=6.81,CHMeMe'), 1.07 (d, 12, J=6.91, CHMeMe'), 0.77 (s, 6, PdMe); ¹³ C NMR(C6D₆, 100 MHz) δ159.9 (J_(CH) =174.5, N═C(H)--C(H)═N), 145.7 (Ar:C_(ipso)), 138.9 (Ar: C_(o)) 127.2 (Ar: C_(p)), 123.4 (Ar: C_(m)), 28.5(CHMe₂),24.4 and 22.8 (CHMeMe'), -5.1 (J_(CH) =128.3, PdMe). Anal. Calcdfor (C₂₈ H₄₂ N₂ Pd): C, 65.55, H, 8.25; N, 5.46. Found: C, 65.14; H,8.12; N, 5.14.

Example 12 (2,6-MePh)₂ DABH₂ !PdMe₂

This compound was synthesized in a manner similar to the secondprocedure of Example 11 (stirred for 5 h at rt) using 5.13 mmol of thecorrespondingdiimine and 2.57 mmol of Me₂ Mg. After the reaction mixturewas filtered, removal of Et₂ O in vacuo yielded 1.29 g (62.2%) of a deepbrown microcrystalline solid: ¹ H NMR (C₆ D₆, 100 MHz, 12° C.) δ6.98 (s,2, N═C(H)--C(H)═N), 6.95 (s, 6, H_(aryl)), 2.13 (s, 12, Ar: Me), 0.77(s, 6, PdMe); ¹³ C NMR (C₆ D₆, 400 MHz, 12° C.) δ160.8 (J_(CH) =174.6,N═C(H)--C(H)═N), 147.8 (Ar: C_(ipso)), 128.2 (Ar: C_(m)), 128.15 (Ar:C_(o)), 126.3 (Ar: C_(p)), 18.2 (Ar: Me), -5.5 (J_(CH) =127.6, Pd--Me).

Example 13 (2,6-i-PrPh)₂ DABH₂ !NiMe₂

The synthesis of this compound has been reported (Svoboda, M.; tomDieck, H. J. Organomet. Chem. 1980, 191, 321-328) and was modified asfollows: A mixture of Ni(acac)₂ (1.89 g, 7.35 mmol) and thecorresponding diimine (2.83 g, 7.51 mmol) was suspended in 75 mL of Et₂O and the suspension was stirred for 1 h at room temperature. Aftercooling the reaction mixture to -78° C., a solution of Me₂ Mg (401 mg,7.37 mmol) in 25 mL of Et₂ O was added via cannula. The reaction mixturewas stirred for 1 h at -78° C. and then for 2 h at 0° C. to give ablue-green solution. After the solution was filtered, the Et₂ O wasremoved in vacuo to give a blue-green brittlefoam. The product was thendissolved in hexane and the resulting solution was filtered twice,concentrated, and then cooled to -30° C. to give 1.23 g (35.9% , onecrop) of small turquoise crystals.

Example 14 (2,6-i-PrPh)₂ DABMe₂ !NiMe₂

The synthesis of this compound has been reported (Svoboda, M.; tomDieck, H. J. Organomet. Chem. 1980, 191, 321-328) and was synthesizedaccording to the above modified procedure (Example 13) using Ni(acac)₂(3.02 g,11.75 mmol), the corresponding diimine (4.80 g, 11.85 mmol) andMe₂ Mg(640 mg, 11.77 mmol). A turquoise powder was isolated (620 mg,10.7%).

Example 15 { (2,6-MePh)₂ DABMe₂ !PdMe(MeCN)}BAF⁻

To a mixture of (2,6-MePh)₂ DABMe₂ !PdMeCl (109.5 mg, 0.244 mmol) andNaBAF (216.0 mg, 0.244 mmol) were added 20 mL each of Et₂ Oand CH₂ Cl₂and 1 mL of CH₃ CN. The reaction mixture was then stirred for 1.5 h andthen the NaCl was removed via filtration. Removal of the solvent invacuo yielded a yellow powder, which was washed with 50 mL of hexane.The product (269.6 mg, 83.8%) was then dried in vacuo: ¹ H NMR (CD₂ Cl₂,400 MHz) δ7.73 (s, 8, BAF: H_(o)), 7.57 (s, 4, BAF: H_(p)), 7.22-7.16(m, 6, H_(aryl)), 2.23 (s, 6, Ar: Me), 2.17 (s, 6, Ar': Me), 2.16, 2.14,and 1.79 (s, 3 each, N═C(Me)--C'(Me)═N, NCMe), 0.38 (s, 3, PdMe); ¹³ CNMR (CD₂ Cl₂, 100 MHz) δ180.1 and 172.2 (N═C--C'═N), 162.1 (q, J_(BC)=49.9, BAF: C_(ipso)), 142.9 (Ar, Ar': C_(o)), 135.2 (BAF: C_(o)), 129.3(Ar: C_(m)), 129.2 (q, J_(CF) =30.6, BAF: C_(m)), 129.0 (Ar': C_(m)),128.4 (Ar: C_(p)), 128.2 (Ar: C_(o)), 127.7 (Ar': C_(p)), 127.4 (Ar':C_(o)), 125.0 (q, J_(CF) =272.4, BAF: CF₃), 121.8 (NCMe), 117.9 (BAF:C_(p)), 20.2 and 19.2 (N═C(Me)--C'(Me)═N), 18.0 (Ar: Me),17.9 (Ar': Me),5.1 and 2.3 (NCMe, PdMe). Anal. Calcd for (C₅₅ H₄₂ BF₂₄ N₃ Pd): C,50.12;H, 3.21; N, 3.19. Found: C, 50.13; H, 3.13, N, 2.99.

Example 16 { (4-MePh)₂ DABMe₂ !PdMe (MeCN)}BAF⁻

Following the procedure of Example 15, a yellow powder was isolated in85% yield: ¹ H NMR (CD₂ Cl₂, 400 MHz) δ7.81 (s, 8, BAF: H_(o)), 7.73 (s,4, BAF: H_(p)), 7.30 (d, 4, J=8.41, Ar, Ar': H_(m)), 6.89 (d, 2, J=8.26,Ar: H_(o)), 6.77 (d, 2, J=8.19, Ar': H_(o)), 2.39 (s, 6, Ar, Ar': Me),2.24, 2.17 and 1.93 (s, 3 each, N═C(Me)--C'(Me)═N, NCMe)Pd--Me; ¹³ C NMR(CD₂ Cl₂, 100 MHz) δ180.7 and 171.6 (N═C--C'═N), 162.1 (q, J_(BC) =49.8,BAF: C_(ipso)), 143.4 and 142.9 (Ar, Ar': C_(ipso)), 138.6 and 138.5(Ar, Ar': C_(p)), 135.2 (BAF: C_(o)), 130.6 and 130.4 (Ar, Ar': C_(m)),129.3 (q, J_(CF) =31.6, BAF: C_(m)) 125.0 (q, J_(CF) =272.5, BAF: CF₃),122.1 (NCMe), 121.0 and 120.9 (Ar, Ar': C_(o)), 117.9 (BAF: C_(p)), 21.5(ArN═C(Me)), 21.1 (Ar, Ar': Me), 19.7 (ArN═C'(Me)), 6.2 and 3.0 (NCMe,PdMe). Anal. Calcd for (C₅₃ H₃₈ BF₂₄ N₃ Pd): C, 49.34; H, 2.97: N, 3.26.Found: C, 49.55; H, 2.93; N, 3.10.

Example 17 (2,6-MePh)₂ DABMe₂ !PdMe (Et₂ O)BAF⁻

A Schlenk flask containing a mixture of (2,6-i-PrPh)₂ DABMe₂ !PdMe₂ (501mg, 0.926 mmol) and H⁺ (OEt₂)₂ BAF⁻ (938 mg, 0.926 mmol) was cooled to-78° C. Following the addition of 50 mL of Et₂ O, the solution wasallowed to warm and stirred briefly (˜15 min) at room temperature. Thesolution was then filtered and the solvent was removed in vacuo to givea pale orange powder(1.28 g, 94.5%), which was stored at -30° C. underan inert atmosphere: ¹ H NMR (CD₂ Cl₂, 400 MHz, -60° C.) δ7.71 (s, 8,BAF: H_(o)), 7.58 (s, 4, BAF: H_(p)), 7.4-7.0 (m, 6, H_(aryl)), 3.18 (q,4, J=7.10, O(CH₂ CH₃)₂), 2.86 (septet, 2, J=6.65, CHMe₂), 2.80 (septet,2, J=6.55, C'HMe₂), 2.18 and 2.15 (N═C(Me)--C'(Me)═N), 1.34, 1.29, 1.14and 1.13 (d, 6each, J=6.4-6.7, CHMeMe', C'HMeMe'), 1.06 (t, J=6.9, O(CH₂CH₃)₂), 0.33 (s, 3, PdMe); ¹³ C NMR (CD₂ Cl₂, 100MHz, -60° C.) δ179.0and 172.1 (N═C--C'═N), 161.4 (q, J_(BC) =49.7, BAF: C_(ipso)), 140.21and 140.15 (Ar, Ar': C_(ipso)),137.7 and 137.4 (Ar, Ar': C_(o)), 134.4(BAF: C_(p)), 128.3 (q, J_(CF) =31.3, BAF: C_(m)), 128.5 and 128.2 (Ar,Ar': C_(p)), 124.2 (q, J_(CF) =272.4, BAF: CF₃), 117.3 (BAF: C_(p)),71.5 (O(CH₂ CH₃)₂), 28.7 (CHMe₂), 28.4 (C'HMe₂), 23.7,23.6, 23.1 and22.6 (CHMeMe', C'HMeMe'), 21.5 and 20.7 (N═C(Me)--C'(Me)═N), 14.2 (O(CH₂CH₃)₂)₂, 8.6 (PdMe). Anal. Calcd for (C₆₅ H₆₅ BF₂₄ N₂ OPd): C, 53.35; H,4.48; N, 1.91. Found: C, 53.01; H, 4.35; N, 1.68.

Example 18 (2,6-MePh)₂ DABH₂ !PdMe (Et₂ O) BAF⁻

Following the procedure of Example 17, an orange powder was synthesizedin 94.3% yield and stored at -30° C.: ¹ H NMR (CD₂ Cl₂,400 MHz, -60° C.)δ8.23 and 8.20 (s, 1 each, N═C(H)--C'(H)═N), 7.72 (s, 8, BAF: H_(o)),7.54 (s, 4, BAF: H_(p)), 7.40-7.27 (m, 6, H_(aryl)), 3.32 (q, 4, J=6.90,O(CH₂ CH₃)₂), 3.04 and 3.01 (septets, 2 each, J=6.9-7.1, CHMe₂ andC'HMe₂), 1.32, 1.318, 1.14 and 1.10 (d, 6 each, J=6.5-6.6, CHMeMe' andC'HMeMe'), 1.21 (t, 6, J=6.93, O(CH₂ CH₃)₂), 0.70 (s, 3, PdMe); ¹³ C NMR(CD₂ Cl₂, 100 MHz, -60° C.) δ166.9 (J_(CH) =182.6, N═C(H)), 161.5(J_(BC) =49.7, BAF: C_(ipso)) 161.3 (J_(CH) =181.6, N═C'(H)), 143.0 and141.8 (Ar, Ar': C_(ipso)) 136.7 and 137.8 (Ar, Ar': C_(o)), 134.4 (BAF:C_(o)), 129.1 and 128.8 (Ar, Ar': C_(p)), 128.3 (J_(CF) =31.3, BAF:C_(m)) 124.0 and 123.9 (Ar, Ar': C_(m)), 117.3 (BAF: C_(p)), 72.0 (O(CH₂CH₃)₂), 28.5 and 28.4 (CHMe₂, C'HMe₂), 25.2, 24.1, 21.9 and 21.7(CHMeMe', C'HMeMe'), 15.2 (O(CH₂ CH₃)₂), 11.4 (J_(CH) =137.8, PdMe).Anal. Calcd for (C₆₃ H₆₁ BF₂₄ N₂ OPd): C, 52.72; H, 4.28; N, 1.95.Found: C, 52.72; H, 4.26; N, 1.86.

Example 19 (2,6-MePh)₂ DABMe₂ !NiMe (Et₂ O) BAF⁻

Following the procedure of Example 17, a magenta powder was isolated andstored at -30° C.: ¹ H NMR (CD₂ Cl₂, 400 MHz, -60° C.; A H₂ O adduct andfree Et₂ O were observed) δ7.73 (s, 8, BAF: H_(o)), 7.55 (s, 4, BAF:H_(p)), 7.4-7.2 (m, 6, H_(aryl)), 3.42 (s, 2, OH₂), 3.22 (q, 4, O(CH₂CH₃)₂), 3.14 and 3.11 (septets, 2 each, J=7.1, CHMe₂, C'HMe₂), 1.95 and1.78 (s, 3 each, N═C(Me)--C'(Me)═N), 1.42, 1.39, 1.18 and 1.11 (d, 6each, J=6.6-6.9, CHMeMe' and C'HMeMe'), 0.93 (t,J=7.5, O(CH₂ CH₃)₂),-0.26 (s,3, NiMe); ¹³ C NMR (CD₂ Cl₂ 100 MHz, -58° C.) δ175.2 and 170.7(N═C--C'═N), 161.6 (q, J_(BC) =49.7, BAF: C_(ipso)), 141.2 (Ar:C_(ipso)), 139.16 and 138.68 (Ar, Ar': C_(o)), 136.8 (Ar': C_(ipso)),134.5 (BAF: C_(o)), 129.1 and 128.4 (Ar, Ar': C_(p)), 128.5 (q, J_(CF)=32.4, BAF: C_(m)), 125.0 and 124.2 (Ar, Ar': C_(m)), 124.3 (q, J_(CF)=272.5, BAF: CF₃), 117.4 (BAF: C_(p)),66.0 (O(CH₂ CH₃)₂), 29.1 (CHMe₂),28.9 (C'HMe₂), 23.51, 23.45, 23.03, and 22.95 (CHMeMe', C'HMeMe'), 21.0and 19.2 (N═C(Me)--C'(Me)═N), 14.2 (OCH₂ CH₃)₂), -0.86 (J_(CH) =131.8,NiMe). Anal. Calcd for (C₆₅ H₆₅ BF₂₄ N₂ NiO): C, 55.15; H, 4.63; N.1.98. Found: C, 54.74; H, 4.53; N, 2.05.

Example 20 (2,6-MePh)₂ DABH₂ !NiMe(Et₂ O)BAF⁻

Following the procedure of Example 17, a purple powder was obtained andstored at -30° C.: ¹ H NMR (CD₂ Cl₂, 400 MHz, -80° C.; H₂ O and Et₂ Oadducts were observed in an 80:20ratio, respectively.) δ8.31 and 8.13(s, 0.8 each, N═C(H)--C'(H)═N; H₂ O Adduct), 8.18 and 8.00 (s, 0.2 each,N═C(H)--C'(H)═N; Et₂ O Adduct), 7.71 (s, 8 BAF: C_(o)), 7.53 (s, 4, BAF:C_(p)), 7.5-7.0 (m, 6, H_(aryl)), 4.21 (s, 1.6, OH₂), 3.5-3.1 (m, 8,O(CH₂ CH₃)₂, CHMe₂, C'HMe₂), 1.38, 1.37, 1.16 and 1.08 (d, 4.8 each,CHMeMe', C'HMeMe'; H₂ O Adduct; These peaks overlap with and obscure theCHMe₂ doublets of the Et₂ O adduct.), 0.27 (s, 2.4, PdMe; H₂ O Adduct),0.12 (s, 0.6, PdMe: Et₂ O Adduct).

Examples 21-23

The rate of exchange of free and bound ethylene was determined by ¹ HNMR line broadening experiments at -85° C. for complex (XI), see theTable below. The NMR instrument was a 400 MHz Varian® NMR spectrometer.Samples were prepared according to the following procedure: Thepalladium ether adducts { (2,6-i-PrPh)₂ DABMe₂ !PdMe(OEt₂)}BAF, {(2,6-i-PrPh)₂ An!PdMe(OEt₂)}BAF, and { (2,6-i-PrPh)₂ DABH₂!PdMe(OEt₂)}BAF were used as precursors to (XI), and were weighed (˜15mg) in a tared 5 mm dia. NMR tube in a nitrogen-filled drybox. The tubewas then capped with a septum and Parafilm® and cooled to -80° C. Dry,degassed CD₂ Cl₂ (700 μL) was then added to the palladium complex viagastight syringe, and the tube was shaken and warmed briefly to give ahomogeneous solution. After acquiring a -85° C. NMR spectrum, ethylenewas added to the solution via gastight syringe and a second NMR spectrumwas acquired at -85° C. The molarity of the BAF counterionwas calculatedaccording to the moles of the ether adduct placed in the NMRtube. Themolarity of (XI) and free ethylene were calculated using the BAF peaksas an internal standard. Line-widths (W) were measured at half-height inunits of Hz for the complexed ethylene signal (usually at 5to 4 ppm) andwere corrected for line widths (W_(o)) in the absence of exchange.

For (XI) the exchange rate was determined from the standard equation forthe slow exchange approximation:

    k=(W-W.sub.o)π/ =!,

where =! is the molar concentration of ethylene. These experiments wererepeated twice and an average value is reported below.

    ______________________________________    Rate Constants for Ethylene Exchange.sup.a                                k    Ex.    (XI)                 (L-M.sup.-1 s.sup.-1)    ______________________________________    21     { (2,6-i-PrPh).sub.2 DABMe.sub.2 !PdMe(=)}BAF                                 45    22     { (2,6-i-PrPh).sub.2 An!PdMe(=)}BAF                                 520    23     { (2,6-i-PrPh).sub.2 DABH.sub.2 !PdMe(=)}BAF                                8100    ______________________________________     .sup.a The T.sub.1 of free ethylene is 15 sec. A pulse delay of 60 sec an    a 30° pulse width were used.

Example 24

Anhydrous FeCl₂ (228 mg, 1.8 mmol) and (2,6-i-PrPh)₂ DABAn (1.0 g, 2.0mmol) were combined as solids and dissolved in 40 ml of CH₂ Cl₂. Themixture was stirred at 25° C. for 4 hr. The resultinggreen solution wasremoved from the unreacted FeCl₂ via filter cannula. The solvent wasremoved under reduced pressure resulting in a green solid (0.95 g, 84%yield).

A portion of the green solid (40 mg) was immediately transferred toanotherSchlenk flask and dissolved in 50 ml of toluene under 1 atm ofethylene. The solution was cooled to 0° C., and 6 ml of a 10% MAOsolution intoluene was added. The resulting purple solution was warmedto 25° C. and stirred for 11 hr. The polymerization was quenched and thepolymer precipitated by acetone. The resulting polymer was washed with6M HCl, water and acetone. Subsequent drying of the polymer resulted in60 mg of white polyethylene. ¹ H NMR (CDCl₃, 200 MHz) δ1.25 (CH₂, CH)δ0.85 (m, CH₃).

Example 25 (2-t-BuPh)₂ DABMe₂

A Schlenk tube was charged with 2-t-butylaniline (5.00 mL, 32.1 mmol)and 2,3-butanedione (1.35 mL, 15.4 mmol). Methanol (10 mL) and formicacid (1 mL) were added and a yellow precipitate began to form almostimmediately upon stirring. The reaction mixture was allowed to stirovernight. The resulting yellow solid was collected via filtration anddried under vacuum. The solid was dissolved in ether and dried over Na₂SO₄ for 2-3 h. The ether solution was filtered, condensed and placedinto the freezer (-30° C.). Yellow crystals were isolated via filtrationanddried under vacuum overnight (4.60 g, 85.7%): ¹ H NMR (CDCl₃, 250MHz)δ7.41(dd, 2H, J=7.7, 1.5 Hz, H_(m)), 7.19 (td, 2H, J=7.5, 1.5 Hz, H_(m)or H_(p)), 7.07 (td, 2H, J=7.6, 1.6 Hz, H_(m) or H_(p)),6.50 (dd, 2H,J=7.7, 1.8 Hz, H_(o)), 2.19 (s, 6H, N═C(Me)--C(Me)═N), 1.34 (s, 18H,C(CH₃)₃).

Examples 26 and 27

General Polymerization Procedure for Examples 26 and 27: In the drybox,a glass insert was loaded with (η³ --C₃ H₅)Pd(μ-Cl)!₂ (11 mg, 0.03mmol), NABAF (53 mg, 0.06 mmol), and an α-diimine ligand (0.06 mmol).The insert was cooled to -35° C. in the drybox freezer, 5 mL of C₆ D₆was added tothe cold insert, and the insert was then capped and sealed.Outside of the drybox, the cold tube was placed under 6.9 MPa ofethylene and allowed to warm to RT as it was shaken mechanically for 18h. An aliquot of the solution was used to acquire a ¹ H NMR spectrum.The remaining portion was added to ˜20 mL of MeOH in order toprecipitate the polymer. The polyethylene was isolated and dried undervacuum

Example 26

α-Diimine was (2,6-i-PrPh)₂ DABMe₂. Polyethylene (50 mg) was isolated asa solid. ¹ H NMR spectrum (C₆ D₆) is consistent with the production of1- and 2-butenes and branched polyethylene.

Example 27

α-Diimine was (2,6-i-PrPh)₂ DABAn. Polyethylene (17 mg) was isolated asa solid. ¹ H NMR spectrum (C₆ D₆) is consistentwith the production ofbranched polyethylene.

Example 28 (2,6-i-PrPh)₂ DABH₂ !NiBr₂

The corresponding diimine (980 mg, 2.61 mmol) was dissolved in 10 mL ofCH₂ Cl₂ in a Schlenk tube under a N₂ atmosphere. This solution was addedvia cannula to a suspension of (DME)NiBr₂ (DME=1,2-dimethoxyethane) (787mg, 2.55 mmol) in CH₂ Cl₂ (20 mL). The resulting red/brown mixture wasstirred for 20 hours. The solventwas evaporated under reduced pressureresulting in a red/brown solid. The product was washed with 3×10 mL ofhexane and dried in vacuo. The product was isolated as a red/brownpowder (1.25 g, 82% yield).

Example 29 (2,6-i-PrPh)₂ DABMe₂ !NiBr₂

Using a procedure similar to that of Example 28, 500 mg (1.62 mmol)(DME)NiBr₂ and 687 mg (1.70 mmol) of the corresponding diimine werecombined. The product was isolated as an orange/brown powder (670 mg,67% yield).

Example 30 (2,6-MePh)₂ DABH₂ !NiBr₂

Using a procedure similar to that of Example 28, 500 mg (1.62 mmol)(DME)NiBr₂ and 448 mg (1.70 mmol) of the corresponding diimine werecombined. The product was isolated as a brown powder (622 mg, 80%yield).

Example 31 (2,6-i-PrPh)₂ DABAn!NiBr₂

Using a procedure similar to that of Example 28, 500 mg (1.62 mmol)(DME)NiBr₂ and 850 mg (1.70 mmol) of the corresponding diimine werecombined. The product was isolated as a red powder (998 mg, 86% yield).Anal. Calcd. for C₃₆ H₄₀ N₂ Br₂ Ni: C, 60.12; H, 5.61;N, 3.89. Found C,59.88; H, 5.20; N, 3.52.

Example 32 (2,6-MePh)₂ DABAn!NiBr₂

The corresponding diimine (1.92 g, 4.95 mmol) and (DME)NiBr₂ (1.5 g,4.86 mmol) were combined as solids in a flame dried Schlenk under anargonatmosphere. To this mixture 30 mL of CH₂ Cl₂ was added giving anorange solution. The mixture was stirred for 18 hours resulting in ared/brown suspension. The CH₂ Cl₂ was removed via filter cannulaleavinga red/brown solid. The product was washed with 2×10 mL of CH₂ Cl₂ anddried under vacuum. The product was obtained as a red/brown powder (2.5g, 83% yield).

Example 33 (2,6-MePh)₂ DABMe₂ !NiBr₂

Using a procedure similar to that of Example 32, the title compound wasmade from 1.5 g (4.86 mmol) (DME)NiBr₂ and 1.45 g (4.95 mmol) of thecorresponding diimine. The product was obtained as a brown powder (2.05g,81% yield).

Example 34 (2,6-i-PrPh)₂ DABMe₂ !PdMeCl

(COD)PdMeCl (9.04 g, 34.1 mmol) was dissolved in 200 ml of methylenechloride. To this solution was added the corresponding diimine (13.79 g,34.1 mmol). The resulting solution rapidly changed color from yellow toorange-red. After stirring at room temperature for several hours it wasconcentrated to form a saturated solution of the desired product, andcooled to -40° C. overnight. An orange solid crystallized from thesolution, and was isolated by filtration, washed with petroleum ether,anddried to afford 12.54 g of the title compound as an orange powder.Second and third crops of crystals obtained from the mother liquorafforded an additional 3.22 g of product. Total yield=87%.

Examples 35-39

The following compounds were made by a method similar to that used inExample 34.

    ______________________________________    Example       Compound    ______________________________________    35             (2,6-I-PrPh).sub.2 DABH.sub.2 !PdMeCl    36             (2,6-i-PrPh).sub.2 DABAn!PdMeCl    37             (Ph).sub.2 DABMe.sub.2 !PdMeCl    38             (2,6-EtPh).sub.2 DABMe.sub.2 !PdMeCl    39             (2,4,6-MePh).sub.2 DABMe.sub.2 !PdMeCl    ______________________________________

Note: The diethyl ether complexes described in Examples 41-46 areunstable in non-coordinating solvents such as methylene chloride andchloroform. They are characterized by ¹ H NMR spectra recorded in CD₃CN; under these conditions the acetonitrile adduct of the Pd methylcation is formed. Typically, less than a whole equivalent of freediethylether is observed by ¹ H NMR when (R)₂ DAB(R')₂ !PdMe(OEt₂)X isdissolved in CD₃ CN. Therefore, it is believed the complexes designatedas "{ (R)₂ DAB(R')₂ !PdMe(OEt₂)}X" below are likely mixtures of { (R)₂DAB(R')₂ !PdMe(OEt₂)}X and (R)₂ DAB(R')₂ !PdMeX, and in the lattercomplexes the X ligand (SbF₆, BF₄, or PF₆) is weakly coordinated topalladium. A formula of the type "{ (R)₂ DAB(R')₂ !PdMe(OEt₂)}X" is a"formal" way of conveying the approximate overall composition of thiscompound, but may not accurately depict the exact coordination to themetal atom.

Listed below are the ¹³ C NMR data for Example 36.

    ______________________________________    .sup.13 C NMR data    TCB, 120C, 0.05M CrAcAc    freq ppm intensity    ______________________________________    46.5568  24.6005    1 cmp and/or 1,3 ccmcc    44.9321  3.42517    1,3 cmc    40.8118  55.4341    2 pmp    40.3658  145.916    1,3 pmp    39.5693  18.458     methylenes from 2 cmp and/or 2 cmc    38.7782  4.16118    38.6295  5.84037    38.2844  8.43098    38.1198  82.9802    37.8384  3.83966    37.5198  13.4977    37.2384  23.4819    37.1163  16.8339    36.7446  114.983    36.0012  6.19217    35.7198  5.17495    34.2278  4.83958    32.9216  20.2781    3B.sub.6 +, 3 EOC    32.619   3.6086    32.4172  2.98497    32.1995  10.637    31.9765  42.2547    31.8809  143.871    30.4686  27.9974    30.3199  47.1951    30.0225  36.1409    29.7411  102.51    29.311   4.83244    28.7111  117.354    28.2597  9.05515    27.1659  22.5725    27.0067  5.81855    26.1146  13.5772    24.5642  2.59695    ββB    22.6368  12.726     2B.sub.5 +, 2 EOC    20.1413  3.7815     2B.sub.3    19.7271  20.0959    1B.sub.1    17.5236  7.01554    end group    14.2528  3.03535    1B.sub.3    13.8812  12.3635    1B.sub.4 +, 1 EOC    ______________________________________

Example 40 { (4-Me₂ NPh)₂ DABMe₂ !PdMe(MeCN}SbF₆.MeCN

A procedure analogous to that used in Example 54, using (4-Me₂ NPh)₂DABMe₂ in place of (2-C₆ H₄ --^(t) Bu)₂ DABMe₂, afforded { (4-NMe₂ Ph)₂DABMe₂ !PdMe(MeCN)}SbF₆.MeCN as a purple solid (product was notrecrystallized in this instance). ¹ H NMR (CD₂ Cl₂) δ6.96 (d, 2H,H_(aryl)), 6.75 (mult, 6H, H_(aryl)), 3.01 (s, 6H,NMe₂), 2.98 (s, 6H,NMe'₂), 2.30, 2.18, 2.03, 1.96 (s's, 3H each,N═CMe, N═CMe', and free andcoordinated N.tbd.CMe), 0.49 (s, 3H, Pd--Me).

Example 41 { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O_(n) }SbF₆ ⁻

(2,6-i-PrPh)₂ DABMe₂ !PdMeCl (0.84 g, 1.49 mmol) was suspended in 50 mLof diethylether and the mixture cooled to -40° C. To this was addedAgSbF₆ (0.52 g, 1.50 mmol). The reaction mixture was allowed to warm toroom temperature, and stirred at room temperature for 90 min. Thereaction mixture was then filtered, giving a pale yellow filtrate and abright yellow precipitate. The yellow precipitate was extracted with4×20 mL 50/50 methylene chloride/diethyl ether. The filtrate andextracts were then combined with an additional 30 mL diethyl ether. Theresulting solution was then concentrated to half its original volume and100 mL of petroleum ether added. The resulting precipitate was filteredoff and dried, affording 1.04 g of the title compound as a yellow-orangepowder (83% yield). ¹ H NMR (CD₃ CN) δ7.30 (mult, 6H, H_(aryl)), 3.37 q,free O(CH₂ CH₃)₂ !, 3.05-2.90 (overlapping sept's, 4H, CHMe₂), 2.20 (s,3H, N═CMe), 2.19 (s, 3H, N═CMe'), 1.35-1.14 (overlapping d's, 24H,CHMe₂), 1.08 (t, free O(CH₂ CH₃)₂ !, 0.28 (s, 3H, Pd--Me). This materialcontained 0.4 equiv of Et₂ O per Pd, as determined by ¹H NMRintegration.

Example 42 { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O)_(n) }BF₄ ⁻

A procedure analogous to that used in Example 41, using AgBF₄ in placeofAgSbF₆, afforded the title compound as a mustard yellow powder in 61%yield. This material contained 0.3 equiv of Et₂ O per Pd, as determinedby ¹ H NMR integration. ¹ H NMR in CD₃ CN was otherwise identical tothat of the compound made in Example 41.

Example 43 { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O)_(n) }PF6⁻

A procedure analogous to that used in Example 41, using AgPF₆ in placeofAgSbF₆, afforded the title compound as a yellow-orange powder in 72%yield. This material contained 0.4 equiv of Et₂ O per Pd, as determinedby ¹ H NMR integration. ¹ H NMR in CD₃ CN was identical to that of thecompound of Example 41.

Example 44 { (2,6-i-PrPh)₂ DABH₂ !PdMe(Et₂ O)_(n) }SbF₆ ⁻

A procedure analogous to that used in Example 41, using(2,6-i-PrPh)₂DABH₂ !PdMeCl in place of (2,6-i-PrPh)₂ DABMe₂ !PdMeCl,afforded the title compound in 71% yield. ¹ H NMR (CD₃ CN) δ8.30 (s, 2H,N═CH and N═CH'), 7.30 (s, 6H, H_(aryl)), 3.37 q, free O(CH₂ CH₃)₂ !,3.15 (br, 4H, CHMe₂), 1.40-1.10 (br, 24H, CHMe₂), 1.08 (t, free O(CH₂CH₃)₂ !, 0.55 (s, 3H, Pd--Me). This material contained 0.5 equiv of Et₂O per Pd, as determined by ¹ H NMR integration.

Example 45 { (₂,4,6 -MePh)₂ DABMe₂ !PdMe(Et₂ O)_(n) }SbF₆ ⁻

(2,4,6-MePh)₂ DABMe₂ !PdMeCl (0.50 g, 1.05 mmol) was partially dissolvedin 40 mL 50/50 methylene chloride/diethylether. To this mixture at roomtemperature was added AgSbF₆ (0.36 g, 1.05 mmol). The resulting reactionmixture was stirred at room temperature for 45 min. It was thenfiltered, and the filtrate concentrated in vacuo to afford an oilysolid. The latter was washed with diethyl ether and dried to afford thetitle compound as a beige powder. ¹ H NMR (CD₃ CN) δ6.99 (s, 4H,H_(aryl)), 3.38 q, free O(CH₂ CH₃)₂ !, 2.30-2.00 (overlapping s's, 24H,N═CMe, N═CMe' and aryl Me's), 1.08 (t, free O(CH₂ CH₃)₂ !, 0.15 (s, 3H,Pd--Me). This material contained 0.7 equiv of Et₂ O per Pd, asdetermined by ¹H MR integration.

Example 46 { (2,6-i-PrPh)₂ DABAn!PdMe(Et₂ O)_(n) }SbF₆ ⁻

A procedure analogous to that used in Example 41, using(2,6-i-PrPh)₂DABAn!PdMeCl in place of (2,6-i-PrPh)₂ DABMe₂ !PdMeCl,afforded the title compound in 92% yield. ¹ H NMR (CD₃ CN) δ8.22 (br t,2H, H_(aryl)), 7.60-7.42 (br mult, 8H, H_(aryl)), 6.93 (br d, 1H,H_(aryl)), 6.53 (br d, 1H, H_(aryl)) 3.38 q, free O(CH₂ CH₃)₂ !, 3.30(br mult, 4H, CHMe₂), 1.36 (br d, 6H, CHMe₂), 1.32 (br d, 6H, CHMe₂),1.08 (t, free O(CH₂ CH₃)₂ !, 1.02 (br d, 6H, CHMe₂), 0.92 (br d, 6H,CHMe₂), 0.68 (s, 3H, Pd--Me). The amount of ether contained in theproduct could not be determined precisely by ¹ H NMR integration, duetooverlapping resonances.

Example 47 (2,6-i-PrPh)₂ DABMe₂ !PdMe(OSO₂ CF₃)

A procedure analogous to that used in Example 41, using AgOSO₂ CF₃ inplace of AgSbF₆, afforded the title compound as a yellow-orange powder.¹ H NMR in CD₃ CN was identical to that ofthe title compound of Example41, but without free ether resonances.

Example 48 { (2,6-i-PrPh)₂ DABMe₂ !PdMe(MeCN)}SbF₆ ⁻

(2,6-i-PrPh)₂ DADMe₂ !PdMeCl (0.40 g, 0.71 mmol) was dissolved in 15 mLacetonitrile to give an orange solution. To this was added AgSbF₆ (0.25g, 0.71 mmol) at room temperature. AgCl immediately precipitated fromthe resulting bright yellow reaction mixture. The mixture was stirred atroom temperature for 3 h. It was then filtered and the AgCl precipitateextracted with 5 mL of acetonitrile. The combined filtrate and extractwere concentrated to dryness affording a yellow solid. This wasrecrystallized from methylene chloride/petroleum ether affording 0.43 gof the title compound as a bright yellow powder (Yield=75%). ¹ H NMR(CDCl₃) δ7.35-7.24 (mult, 6H, H_(aryl)), 2.91 (mult, 4H, CHMe₂), 2.29(s, 3H, N═CMe), 2.28 (s, 3H, N═CMe'), 1.81 (s, 3H, N.tbd.CMe), 1.37-1.19(overlapping d's, 24H, CHMe's), 0.40 (s, 3H, Pd--Me). This compound canalso be prepared by addition of acetonitrile to { (2,6-i-PrPh)₂ DABMe₂!PdMe(Et₂ O)}SbF₆ ⁻.

Example 49 { (Ph)₂ DABMe₂ !PdMe(MeCN)}SbF₆ ⁻

A procedure analogous to that used in Example 48, using (Ph)₂ DABMe₂!PdMeCl in place of (2,6-i-PrPh)₂ DABMe₂ !PdMeCl, afforded the titlecompound as a yellow microcrystalline solid upon recrystallization frommethylene chloride/petroleum ether. This complex crystallizes as theacetonitrile solvate from acetonitrile solution at -40° C. ¹ H NMR ofmaterial recrystallized from methylene chloride/petroleum ether: (CDCl₃)δ7.46 (mult, 4H, H_(aryl)),7.30 (t, 2H, H_(aryl)), 7.12 (d, 2H,H_(aryl)), 7.00 (d, 2H, H_(aryl)), 2.31 (s, 3H, N═CMe), 2.25 (s, 3H,N═CMe'), 1.93 (s, 3H, N.tbd.CMe), 0.43 (s, 3H, Pd--Me).

Example 50 { (2,6-EtPh)₂ DABMe₂ !PdMe(MeCN)}BAF⁻

(2,6-EtPh)₂ DABMe₂ !PdMeCl (0.200 g, 0.396 mmol) was dissolved in 10 mLof acetonitrile to give an orange solution. To this was added NaBAF(0.350 g, 0.396 mmol). The reaction mixture turned bright yellow andNaClprecipitated. The reaction mixture was stirred at room temperature for30min and then filtered through a Celite® pad. The Celite® padwasextracted with 5 mL of acetonitrile. The combined filtrate andextract was concentrated in vacuo to afford an orange solid,recrystallization of which from methylene chloride/petroleum ether at-40° C. afforded 0.403 g of the title compound as orange crystals(Yield=74%). ¹ H NMR(CDCl₃) δ7.68 (s, 8H, H_(ortho) of anion), 7.51 (s,4H, H_(para) of anion), 7.33-7.19 (mult, 6H, H_(aryl) of cation),2.56-2.33 (mult, 8H, CH₂ CH₃), 2.11 (s, 3H, N═CMe), 2.09 (s,3H, N═CMe'),1.71 (s, 3H, N.tbd.CMe), 1.27-1.22 (mult, 12H, CH₂ CH₃), 0.41 (s, 3H,Pd--Me).

Example 51 { (2,6-EtPh)₂ DABMe₂ !PdMe(MeCN)}SbF₆ ³¹

A procedure analogous to that used in Example 50, using AgSbF₆ in placeof NaBAF, afforded the title compound as yellow crystals in 99% yieldafter recrystallization from methylene chloride/petroleum ether at -40°C.

Example 52 (COD)PdMe(NCMe)!SbF₆ ⁻

To (COD)PdMeCl (1.25 g, 4.70 mmol) was added a solution of acetonitrile(1.93 g, 47.0 mmol) in 20 mL methylene chloride. To this clear solutionwas added AgSbF₆ (1.62 g, 4.70 mmol). A white solid immediatelyprecipitated. The reaction mixture was stirred at room temperature for45 min, and then filtered. The yellow filtrate was concentrated todryness, affording a yellow solid. This was washed with ether and dried,affording 2.27 g of (COD)PdMe(NCMe)!SbF₆ ⁻ as a light yellow powder(yield=95%). ¹ H NMR (CD₂ Cl₂) δ5.84 (mult, 2H, CH═CH), 5.42 (mult, 2H,CH'═CH'), 2.65 (mult, 4H, CHH'), 2.51 (mult, 4H, CHH'), 2.37 (s, 3H,NCMe), 1.18 (s, 3H, Pd--Me).

Example 53 (COD)PdMe(NCMe)!BAF⁻

A procedure analogous to that used in Example 52, using NaBAF in placeof AgSbF₆, afforded the title compound as a light beige powder in 96%yield.

Example 54 { (2-t-BuPh)₂ DABMe₂ !PdMe(MeCN)}SbF₆ ⁻

To a suspension of (2-t-BuPh)₂ DABMe₂ (0.138 g, 0.395 mmol) in 10mL ofacetonitrile was added (COD)PdMe(NCMe)!SbF₆ (0.200 g, 0.395 mmol). Theresulting yellow solution was stirred at room temperature for 5min. Itwas then extracted with 3×10 mL of petroleum ether. The yellowacetonitrile phase was concentrated to dryness, affording a brightyellow powder. Recrystallization from methylene chloride/petroleum etherat -40° C. afforded 180 mg of the title product as a bright yellowpowder (yield=61%). ¹ H NMR (CD₂ Cl₂) δ7.57 (dd, 2H, H_(aryl)), 7.32(mult, 4H, H_(aryl)), 6.88 (dd, 2H, H_(aryl)), 6.78 (dd, 2H, H_(aryl)),2.28 (s, 3H, N═CMe), 2.22 (s, 3H, N═CMe'), 1.78 (s, 3H, N.tbd.CMe), 1.48(s, 18H, ^(t) Bu), 0.52 (s, 3H, Pd--Me).

Example 55 { (Np)₂ DABMe₂ !PdMe(MeCN)}SbF₆ ⁻

A procedure analogous to that used in Example 54, using (Np)₂ DABMe₂ inplace of (2-t-BuPh)₂ DABMe₂, afforded the title compound as an orangepowder in 52% yield after two recrystallizations from methylenechloride/petroleum ether. ¹ H NMR (CD₂ Cl₂) δ8.20-7.19 (mult, 14H,H_(aromatic)), 2.36 (d, J=4.3 Hz, 3H, N═CMe), 2.22 (d, J=1.4 Hz, 3H,N═CMe'), 1.32 (s, 3H, NCMe), 0.22 (s, 3H, Pd--Me).

Example 56 { (Ph₂ CH)₂ DABH₂ !PdMe(MeCN)}SbF₆ ⁻

A procedure analogous to that used in Example 54, using (Ph₂ CH)₂DABH₂in place of (2-t-BuPh)₂ DABMe₂, afforded the title compound as a yellowmicrocrystalline solid. ¹ H NMR (CDCl₃) δ7.69 (s, 1H, N═CH), 7.65 (s,1H, N═CH'), 7.44-7.08 (mult, 20H, H_(aryl)), 6.35 (2, 2H, CHPh₂), 1.89(s, 3H, NCMe), 0.78 (s, 3H, Pd--Me).

Example 57 { (2-PhPh)₂ DABMe₂ !PdMe(MeCN)}SbF₆ ⁻

A procedure analogous to that used in Example 54, using (2-PhPh)₂ DABMe₂in place of (2-t-BuPh)₂ DABMe₂, afforded the title compound as ayellow-orange powder in 90% yield. Two isomers, due to cis or transorientations of the two ortho phenyl groups on either side of thesquareplane, were observed by ¹ H NMR. ¹ H NMR (CD₂ Cl₂) δ7.80-6.82 (mult,18H, H_(aryl)), 1.98, 1.96, 1.90, 1.83, 1.77, 1.73 (singlets, 9H, N═CMe,N═CMe', NCMe for cis and trans isomers), 0.63, 0.61 (singlets, 3H,Pd--Me for cis and trans isomers).

Example 58 { (Ph)₂ DAB(cyclo-CMe₂ CH₂ CMe₂ --)!PdMe(MeCN)}BAF.sup.-

To a solution of (COD)PdMe(NCMe)!BAF⁻ (0.305 g, 0.269 mmol) dissolvedin15 mL of acetonitrile was addedN,N'-diphenyl-2,2',4,4'-tetramethyl-cyclopentyldiazine (0.082 g, 0.269mmol). A gold colored solution formed rapidly and was stirred at roomtemperature for 20 min. The solution was then extracted with 4×5 mLpetroleum ether, and the acetonitrile phase concentrated to dryness toafford a yellow powder. This was recrystallized from methylenechloride/petroleum ether at -40° C. to afford 0.323 g (90%) of the titlecompound as a yellow-orange, crystalline solid. ¹ H NMR (CDCl₃) δ7.71(s, 8H, H_(ortho) of anion), 7.54 (s, 4H, H_(para) of anion), 7.45-6.95(mult, 10H, H_(aryl) of cation), 1.99 (s, 2H, CH₂), 1.73 (s, 3H, NCMe),1.15 (s, 6H, Me₂), 1.09 (s, 6H, Me'₂), 0.48 (s, 3H, Pd--Me).

Example 59 { (2,6-i-PrPh)₂ DABMe₂ !Pd(CH₂ CH₂ CH₂ CO₂ Me)}SbF₆ ⁻

Under a nitrogen atmosphere { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂O)}SbF₆ ⁻(3.60 g, 4.30 mmol) was weighed into a round bottom flask containing amagnetic stirbar. To this was added a -40° C. solution of methylacrylate (1.85 g, 21.5 mmol) dissolved in 100 ml of methylene chloride.The resulting orange solution was stirred for 10 min, while beingallowed to warm to room temperature. The reaction mixture was thenconcentrated to dryness, affording a yellow-brown solid. The crudeproduct was extracted with methylene chloride, and the orange-redextract concentrated, layered with an equal volume of petroleum ether,and cooled to -40° C. This afforded 1.92 g of the title compound asyellow-orange crystals. An additional 1.39 g was obtained as a secondcropfrom the mother liquor; total yield=91%. ¹ H NMR (CD₂ Cl₂)δ7.39-7.27 (mult, 6H, H_(aryl)), 3.02 (s, 3H, OMe), 2.97 (sept, 4H,CHMe₂), 2.40 (mult, 2H, CH₂), 2.24 (s, 3H, N═CMe), 2.22 (s, 3H, N═CMe'),1.40-1.20 (mult, 26H, CHMe₂ and CH₂ '), 0.64 (mult, 2H, CH₂ ").

Example 60 { (2,6-i-PrPh)₂ DABH₂ !Pd(CH₂ CH₂ CH₂ CO₂ Me)}SbF₆ ⁻

AgSbF₆ (0.168 g, 0.489 mmol) was added to a -40° C. solution of {(2,6-i-PrPh)₂ DABH₂ !PdMeCl (0.260 g, 0.487 mmol) and methyl acrylate(0.210 g, 2.44 mmol) in 10 mL methylene chloride. The reaction mixturewas stirred for 1 h while warming to room temperature, and thenfiltered. The filtrate was concentrated in vacuo to give a saturatedsolution of the title compound, which was then layered with an equalvolume of petroleum ether and cooled to -40° C. Red-orangecrystalsprecipitated from the solution. These were separated byfiltration and dried, affording 0.271 g of the title compound (68%yield). ¹ H NMR (CD₂ Cl₂) δ8.38 (s, 1H, N═CH), 8.31 (s, 1H, N═CH'),7.41-7.24 (mult, 6H, H_(aryl)), 3.16 (mult, 7H, OMe and CHMe₂), 2.48(mult, 2H, CH₂), 1.65 (t, 2H, CH₂ '), 1.40-1.20 (mult, 24H, CHMe₂), 0.72(mult, 2H, CH₂ ").

Example 61 { (2,6-i-PrPh)₂ DABMe₂ !Pd(CH₂ CH₂ CH₂ CO₂ Me)} B(C₆ F₅)₃ Cl!

(2,6-i-PrPh)₂ DABMe₂ !PdMeCl (0.038 g, 0.067 mmol) and methyl acrylate(0.028 g, 0.33 mmol) were dissolved in CD₂ Cl₂. To thissolution wasadded B(C₆ F₅)₃ (0.036 g, 0.070 mmol). ¹ HNMR of the resulting reactionmixture showed formation of the title compound.

Example 62

A 100 mL autoclave was charged with chloroform (50 mL), { (2-t-BuPh)₂DABMe₂ !PdMe(NCMe)}SbF₆ ⁻ (0.090 g, 0.12 mmol), and ethylene(2.1 MPa).The reaction mixture was stirred at 25° C. and 2.1 MPa ethylene for 3 h.The ethylene pressure was then vented and volatiles removed from thereaction mixture in vacuo to afford 2.695 g of branched polyethylene.The number average molecular weight (M_(n)), calculated by ¹ H NMRintegration of aliphatic vs. olefinic resonances, was 1600. The degreeof polymerization, DP, was calculated on the basis of the ¹ H NMRspectrum to be 59; for a linear polymer this would result in 18methyl-ended branches per 1000 methylenes. However, based on the ¹H NMRspectrum the number of methyl-ended branches per 1000 methylenes wascalculated to be 154. Therefore, it may be concluded that this materialwas branched polyethylene. ¹ H NMR (CDCl₃) δ5.38 (mult, vinyl H's) 1.95(mult, allylic methylenes), 1.62 (mult, allylic methyls), 1.24 (mult,non-allylic methylenes and methines), 0.85 (mult, non-allylic methyls).

Example 63

A suspension of { (2-t-BuPh)₂ DABMe₂ !PdMe(NCMe)}SbF₆ ⁻ (0.015 g, 0.02mmol) in 5 mL FC-75 was agitated under 2.8 MPa of ethylene for 30 min.The pressure was then increased to 4.1 MPa and maintained at thispressure for 3 h. During this time the reaction temperature variedbetween 25° and 40° C. A viscous oil was isolated from the reactionmixture by decanting off the FC-75 and dried in vacuo. The numberaveragemolecular weight (M_(n)), calculated by ¹ H NMR integration of aliphaticvs. olefinic resonances, was 2600. DP for this material was calculatedon the basis of the ¹ H NMR spectrum to be 95; for a linear polymer thiswould result in 11 methyl-ended branches per 1000 methylenes. However,based on the ¹ H NMR spectrum the number of methyl-ended branches per1000 methylenes was calculated to be 177.

Example 64

A 100 mL autoclave was charged with chloroform (55 mL), { (2-PhPh)₂DABMe₂ !PdMe(NCMe)}SbF₆ ⁻ (0.094 g, 0.12 mmol), and ethylene(2.1 MPa).The reaction mixture was stirred at 25° C. and 2.1 MPa ethylene for 3 h.The ethylene pressure was then vented and volatiles removed from thereaction mixture in vacuo to afford 2.27 g of a pale yellow oil. Mn wascalculated on the basis of ¹ H NMR integration of aliphatic vs. olefinicresonances to be 200. The degree of polymerization,DP, was calculated onthe basis of the ¹ H NMR spectrum to be 7.2; fora linear polymer thiswould result in 200 methyl-ended branches per 1000 methylenes. However,based on the ¹ H NMR spectrum the number of methyl-ended branches per1000 methylenes was calculated to be 283.

Example 65

A suspension of (2-PhPh)₂ DABMe₂ !PdMe(NCMe)}SbF₆ ⁻ (0.016 g, 0.02 mmol)in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h 40 min.During this time the reaction temperature varied between 23° and 41° C.A viscous oil (329 mg) was isolated from the reaction mixture bydecanting off the FC-75 and dried in vacuo. Mn was calculated on thebasis of ¹ H NMR integration of aliphatic vs. olefinic resonances to be700. The degree of polymerization, DP, was calculated on the basis ofthe ¹ H NMR spectrum to be 24.1; for a linear polymer this would resultin 45 methyl-ended branches per 1000 methylenes. However, based on the ¹H NMR spectrum the number of methyl-ended branches per 1000 methyleneswas calculated to be 173.

Example 66

A 100 mL autoclave was charged with FC-75 (50 mL), {(Ph₂DABMe₂)PdMe(NCMe)}SbF₆ ⁻ (0.076 g, 0.12 mmol) and ethylene (2.1 MPa).The reaction mixture was stirred at 24° C. for 1.5 h. The ethylenepressure was then vented, and the FC-75 mixture removed from thereactor. A small amount of insoluble oil was isolated from the, mixtureby decanting off the FC-75. The reactor was washed out with 2×50 mLCHCl₃, and the washings added to the oil. Volatiles removed from theresulting solution in vacuo to afford 144 mg of an oily solid. Mn wascalculated on the basis of ¹ H NMR integration of aliphatic vs. olefinicresonances to be 400. The degree of polymerization,DP, was calculated onthe basis of the ¹ H NMR spectrum to be 13.8; for a linear polymer thiswould result in 83 methyl-ended branches per 1000 methylenes. However,based on the ¹ H NMR spectrum the number ofmethyl-ended branches per1000 methylenes was calculated to be 288.

Example 67

A 100 mL autoclave was charged with chloroform (50 mL), { (2,6-EtPh)₂DABMe₂ !PdMe(NCMe)}BAF⁻ (0.165 g, 0.12 mmol), and ethylene (2.1 MPa).The reaction mixture was stirred under 2.1 MPa of ethylene for 60 min;during this time the temperature inside the reactor increased from 22°to 48° C. The ethylene pressure was then vented and volatiles removedfrom the reaction mixture in vacuo to afford 15.95 g of a viscous oil. ¹H NMR of this material showed it to be branched polyethylene with 135methyl-ended branches per 1000 methylenes. GPC analysis intrichlorobenzene (vs. a linear polyethylene standard) gave Mn=10,400,M_(w) =22,100.

Example 68

This was run identically to Example 67, but with { (2,6-EtPh)₂ DABMe₂!PdMe(NCMe)}SbF₆ ⁻ (0.090 g, 0.12 mmol) in place of the correspondingBAF salt. The temperature of the reaction increased from23° to 30° C.during the course of the reaction. 5.25 g of a viscous oil was isolated,¹ H NMR of which showed it to be branched polyethylene with 119methyl-ended branches per 1000 methylenes.

Example 69

A suspension of { (Np)₂ DABMe₂ !PdMe(NCMe)}SbF₆ ⁻ (0.027g, 0.02 mmol) in5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h;during thistime the temperature inside the reactor varied between 25° and 40° C.Two FC-75 insoluble fractions were isolated from the reaction mixture.One fraction, a non-viscous oil floating on topof the FC-75, was removedby pipette and shown by ¹ H NMR to be branched ethylene oligomers forwhich Mn=150 and with 504 methyl-ended branches per 1000 methylenes. Theother fraction was a viscous oil isolated by removing FC-75 by pipette;it was shown by ¹ H NMR to be polyethylene for which M_(n) =650 and with240 methyl-ended branches per1000 methylenes.

Example 70

A suspension of { (Ph₂ CH)₂ DABH₂ !PdMe(NCMe)}SbF₆ ⁻ (0.016 g, 0.02mmol) in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h 40min. During this time the reaction temperature varied between 23° and41° C. A viscousoil (43 mg) was isolated from the reaction mixture bydecanting off the FC-75 and dried in vacuo. Mn was calculated on thebasis of ¹ H NMR integration of aliphatic vs. olefinic resonances to beapproximately 2000.The degree of polymerization, DP, was calculated onthe basis of the ¹H NMR spectrum to be 73; for a linear polymer thiswould result in 14 methyl-ended branches per 1000 methylenes. However,based on the ¹ H NMR spectrum the number of methyl-ended branches per1000 methylenes was calculated to be 377.

Example 71

A 100 mL autoclave was charged with FC-75 (50 mL), ({Ph₂ DAB(cyclo--CMe₂ CH₂ CMe₂ --)}PdMe(MeCN))BAF⁻ (0.160 g, 0.12 mmol) and ethylene(2.1 MPa). The reaction mixture was stirred at 24°-25° C. for 3.5 h. Theethylene pressure was then vented,and the cloudy FC-75 mixture removedfrom the reactor. The FC-75 mixture was extracted with chloroform, andthe chloroform extract concentrated to dryness affording 0.98 g of anoil. Mn was calculated on the basis of ¹ H NMR integration of aliphaticvs. olefinic resonances to be 500. The degree of polymerization, DP, wascalculated on the basis of the ¹ H NMR spectrum to be 19.5; for a linearpolymer this would result in 57 methyl-ended branches per 1000methylenes. However, based on the ¹ H NMR spectrum the number ofmethyl-ended branches per 1000 methylenes was calculated to be 452.

Example 72

A 100 mL autoclave was charged with FC-75 (50 mL), { (4-NMe₂ Ph)₂DABMe₂!PdMe(MeCN)}SbF₆ ⁻ (MeCN) (0.091 g, 0.12 mmol) and ethylene (2.1 MPa).The reaction mixture was stirred at 24° C. for 1.5 h. The ethylenepressure was then vented, and the cloudy FC-75 mixtureremoved from thereactor. The FC-75 was extracted with 3×25 mL of chloroform. The reactorwas washed out with 3×40 mL CHCl₃, and the washings added to theextracts. Volatiles removed from the resulting solution in vacuo toafford 556 mg of an oil. Mn was calculated on the basis of ¹ H NMRintegration of aliphatic vs. olefinic resonances to be 200. The degreeof polymerization, DP, was calculated on the basis of the ¹ H NMRspectrum to be 8.4; for a linear polymer this would result in 154methyl-ended branches per 1000 methylenes. However, based onthe ¹ H NMRspectrum the number of methyl-ended branches per 1000 methylenes wascalculated to be 261.

Example 73

Under nitrogen, a 250 mL Schlenk flask was charged with 10.0 g of themonomer CH₂ ═CHCO₂ CH₂ CH₂ (CF₂)_(n) CF₃ (avg n=9), 40 mL of methylenechloride, and a magnetic stirbar. To the rapidly stirred solution wasadded (2,6-i-PrPh)₂ DABMe₂ !PdMe(OEt₂)}SbF₆ ⁻ (0.075 g, 0.089 mmol) insmall portions. The resulting yellow-orange solution was stirred under 1atm of ethylene for 18 h. The reaction mixture was then concentrated,and the viscous product extracted with ˜300 mL of petroleum ether. Theyellow filtrate was concentrated to dryness, and extracted a second timewith ˜150 mL petroleum ether. ˜500 mL of methanol was added to thefiltrate; the copolymer precipitated as an oil which adhered to thesides of the flask, and was isolated by decanting off the petroleumether/methanol mixture. The copolymer was dried, affording 1.33 g of aslightly viscous oil. Upon standing for several hours, an additional0.70 g of copolymer precipitated from the petroleum ether/methanolmixture. By ¹ H NMR integration, it was determined that the acrylatecontent of this material was 4.2 mole %, and that it contained 26 esterand 87 methyl-ended branches per 1000 methylenes. GPC analysis intetrahydrofuran(vs. a PMMA standard) gave M_(n) =30,400, M_(w) =40,200.¹ H NMR (CDCl₃) δ4.36 (t, CH₂ CH₂ CO2CH₂ CH₂ R_(f)), 2.45 (mult, CH₂ CH₂CO2CH₂ CH₂ R_(f)), 2.31 (t, CH₂ CH₂ CO2CH₂ CH₂ R_(f)), 1.62 (mult, CH₂CH₂ CO2CH₂ CH₂ R_(f)), 1.23 (mult, other methylenes and methines), 0.85(mult, methyls). ¹³ C NMR gave branching per 1000 CH₂ : Total methyls(91.3), Methyl (32.8), Ethyl(20), Propyl (2.2), Butyl (7.7), Amyl (2.2),≧Hex and end of chains (22.1). GPC analysis in THF gave Mn=30,400,Mw=40,200 vs. PMMA.

Example 74

A 100 mL autoclave was charged with Pd(CH₃ CH₂ CN)₄ !(BF₄)₂ (0.058 g,0.12 mmol) and chloroform (40 mL). To this wasadded a solution of(2,6-i-PrPh)₂ DABMe₂ (0.070 g, 0.17 mmol) dissolved in 10 mL ofchloroform under ethylene pressure (2.1 MPa). The pressure wasmaintained at 2.1 MPa for 1.5 h, during which time the temperatureinside the reactor increased from 22° to 35° C. The ethylene pressurewas then vented and the reaction mixture removed from the reactor. Thereactor was-washed with 3×50 mL of chloroform,the washings added to thereaction mixture, and volatiles removed from the resulting solution invacuo to afford 9.77 g of a viscous oil. ¹ H NMR of this material showedit to be branched polyethylene with 96 methyl-ended branches per 1000methylenes.

Example 75

A 100 mL autoclave was charged with Pd(CH₃ CN)₄ !(BF₄)₂ (0.053 g, 0.12mmol) and chloroform (50 mL). To this wasadded a solution of(2,6-i-PrPh)₂ DABMe₂ (0.070 g, 0.17 mmol) dissolved in 10 mL ofchloroform under ethylene pressure (2.1 MPa). The pressure wasmaintained at 2.1 MPa for 3.0 h, during which time the temperatureinside the reactor increased from 23° to 52° C. The ethylene pressurewas then vented and the reaction mixture removed from the reactor. Thereactor was washed with 3×50 mL of chloroform,the washings added to thereaction mixture, and volatiles removed from the resulting solution invacuo to afford 25.98 g of a viscous oil. ¹ H NMR of this materialshowed it to be branched polyethylene with 103 methyl-ended branches per1000 methylenes. GPC analysis in trichlorobenzene gave M_(n) =10,800,M_(w) =21,200 vs. linear polyethylene.

Example 76

A mixture of 20 mg (0.034 mmol) of (2,6-i-PrPh)DABH₂ !NiBr₂ and 60 mLdry, deaerated toluene was magnetically-stirred under nitrogen in a200-mL three-necked flask with a gas inlet tube, a thermometer, and agas exit tube which vented through a mineral oil bubbler. To thismixture, 0.75 mL (65 eq) of 3M poly(methylalumoxane) (PMAO) in toluenewas added via syringe. The resulting deep blue-black catalyst solutionwas stirred as ethylene was bubbled through at about 5 ml and 1 atm for2 hr. The temperature of the mixture rose to 60° C. in the first 15 minand then dropped to room temperature over the course of the reaction.

The product solution was worked up by blending with methanol; theresultingwhite polymer was washed with 2N HCl, water, and methanol toyield after drying (50° C./vacuum/nitrogen purge) 5.69 g (6000 catalystturnovers) of polyethylene which was easily-soluble in hotchlorobenzene. Differential scanning calorimetry exhibited a broadmelting point at 107° C. (67 J/g). Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n) =22,300; M_(w)=102,000; M_(w) /M_(n) =4.56. ¹³ C NMR analysis: branching per 1000 CH₂: total Methyls (60), Methyl (41), Ethyl (5.8), Propyl (2.5), Butyl(2.4), Amyl (1.2), ≧Hexyl and end of chain (5); chemical shifts werereferenced to the solvent: the high field carbon of1,2,4-trichlorobenzene (127.8 ppm). A film of polymer (pressed at 200°C.) was strong and could be stretched and drawn without elasticrecovery.

Example 77

In a Parr® 600-mL stirred autoclave under nitrogen was combined 23 mg(0.039 mmol) of (2,6-i-PrPh)DABH₂ !NiBr₂, 60 mL of dry toluene,and 0.75mL of poly(methylalumoxane) at 28° C. The mixture was stirred, flushedwith ethylene, and pressurized to 414 kPa with ethylene. The reactionwas stirred at 414 kPa for 1 hr; the internal temperature rose to 31° C.over this time. After 1 hr, the ethylene was vented and 200 mL ofmethanol was added with stirring to the autoclave. The resulting polymerslurry was filtered; the polymer adhering to the autoclave walls andimpeller was scraped off and added to the filtered polymer. The productwas washed with methanol and acetone and dried (80° C./vacuum/nitrogenpurge) to yield 5.10 g (4700 catalyst turnovers) of polyethylene.Differential scanning calorimetry exhibited a melting point at 127° C.(170 J/g). Gel permeation chromatography (trichlorobenzene, 135° C.,polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n) =49,300; M_(w) =123,000; M_(w)/M_(n) =2.51. Intrinsic viscosity (trichlorobenzene, 135° C.): 1.925dL/g. Absolute molecular weight averages corrected for branching: M_(n)=47,400; M_(w) =134,000; M_(w) /M_(n) =2.83. ¹³ C NMR analysis;branching per 1000 CH₂ : total Methyls (10.5), Methyl (8.4), Ethyl(0.9), Propyl (0), Butyl (0), ≧Butyl and end of chain (1.1); chemicalshifts were referenced to the solvent: the high field carbon of1,2,4-trichlorobenzene(127.8 ppm). A film of polymer (pressed at 200°C.) was strong and stiff and could be stretched and drawn withoutelastic recovery. This polyethylene is much more crystalline and linearthan the polymer of Example 76. This example shows that only a modestpressure increase from 1atm to 414 kPa allows propagation tosuccessfully compete with rearrangement and isomerization of the polymerchain by this catalyst, thus giving a less-branched, more-crystallinepolyethylene.

Example 78

A mixture of 12 mg (0.020 mmol) of (2,6-i-PrPh)DABH₂ !NiBr₂ and 40 mLdry, deaerated toluene was magnetically-stirred under nitrogen at 15° C.in a 100-mL three-necked flask with an addition funnel, a thermometer,and a nitrogen inlet tube which vented through a mineral oil bubbler. Tothis mixture, 0.5 mL of poly(methylalumoxane) in toluene was added viasyringe; the resulting burgundy catalyst solution was stirred for 5 minand allowed to warm to room temperature. Into the addition funnel wascondensed (via a Dry Ice condenser on the top of the funnel) 15mL (about10 g) of cis-2-butene. The catalyst solution was stirred as thecis-2-butene was added as a liquid all at once, and the mixture wasstirred for 16 hr. The product solution was treated with 1 mL ofmethanol and was filtered through diatomaceous earth; rotary evaporationyielded 0.35 g (300 catalyst turnovers) of a light yellow grease,poly-2-butene. ¹³ C NMR analysis; branching per 1000 CH₂ : total Methyls(365),Methyl (285), Ethyl (72), ≧Butyl and end of chain (8); chemicalshifts were referenced to the solvent chloroform-d₁ (77 ppm).

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    CDCl.sub.3, RT, 0.05M CnAcAc    Freq ppm  Intensity    ______________________________________    41.6071   11.2954    41.1471   13.7193    38.6816   3.55568    37.1805   7.07882    36.8657   33.8859    36.7366   35.1101    36.6196   33.8905    36.2645   12.1006    35.9094   13.3271    35.8004   11.8845    35.5785   4.20104    34.7351   24.9682    34.4325   39.3436    34.3114   59.2878    34.1177   125.698    33.9886   121.887    33.8837   120.233    33.5326   49.8058    33.004    132.842    32.7377   51.2221    32.657    55.6128    32.3705   18.1589    31.5876   9.27643    31.3818   16.409    31.0066   15.1861    30.0946   41.098    29.9736   42.8009    29.7072   106.314    29.3602   60.0884    29.2512   35.0694    29.114    26.6437    28.9769   29.1226    27.9358   3.57351    27.7501   3.56527    27.0682   14.6121    26.7333   81.0769    26.3257   14.4591    26.015    11.8399    25.3008   8.17451    25.0627   5.98833    22.4801   3.60955         2B.sub.4    22.3308   10.4951         2B.sub.5 +, EOC    19.6192   90.3272         1B.sub.1    19.4618   154.354         1B.sub.1    19.3085   102.085         1B.sub.1    18.9937   34.7667         1B.sub.1    18.8525   38.7651         1B.sub.1    13.7721   11.2148         1B.sub.4 +, EOC, 1B.sub.3    11.0484   54.8771         1B.sub.2    10.4552   10.8437         1B.sub.2    10.1283   11.0735         1B.sub.2    9.99921   9.36226         1B.sub.2    ______________________________________

Example 79

A mixture of 10 mg (0.017 mmol) of (2,6-i-PrPh)DABH₂ !NiBr₂ and 40 mLdry, deaerated toluene was magnetically-stirred under nitrogen at 5° C.in a 100-mL three-necked flask with an addition funnel, a thermometer,and a nitrogen inlet tube which vented through a mineral oil bubbler. Tothis mixture, 0.5 mL of 3M poly(methylalumoxane) in toluene was addedvia syringe; the resulting burgundy catalyst solution was stirred at 5°C. for 40 min. Into the addition funnel was condensed(via a Dry Icecondenser on the top of the funnel) 20 mL (about 15 g) of 1-butene. Thecatalyst solution was stirred as the 1-butene was added as aliquid allat once. The reaction temperature rose to 50° C. over 30 min and thendropped to room temperature as the mixture was stirred for 4 hr. Theproduct solution was treated with 1 mL of methanol and was filteredthrough diatomaceous earth; rotary evaporation yielded 6.17 g (1640catalyst turnovers) of clear, tacky poly-1-butene rubber. Gel permeationchromatography (trichlorobenzene, 135° C., polystyrene reference,results calculated as polyethylene using universal calibration theory):M_(n) =64,700; M_(w) =115,000; M_(w) /M_(n) =1.77. ¹³ C NMR analysis;branching per 1000 CH₂ : total Methyls (399),Methyl (86), Ethyl (272),≧Butyl and end of chain (41); chemical shifts were referenced to thesolvent chloroform-d₁ (77 ppm). This example demonstrates thepolymerization of an alpha-olefin and shows the differences in branchingbetween a polymer derived from a 1-olefin (this example) and a polymerderived from a 2-olefin (Example 78). This difference shows that theinternal olefin of Example 78 is not first isomerized to an alpha-olefinbefore polymerizing; thus this catalyst is truly able to polymerizeinternal olefins.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    CDCl.sub.3, RT, 0.05M CrAcAc    Freq ppm  Intensity    ______________________________________    43.8708   6.42901    41.5304   11.1597    41.0825   16.1036    38.7623   103.647    38.1247   50.3288    37.3338   24.6017    36.8173   30.0925    35.756    55.378    35.0337   22.3563    34.1419   64.8431    33.8514   55.3508    33.4116   90.2438    33.0645   154.939    32.7094   51.3245    32.431    23.0013         3B.sub.5    30.946    12.8866         3B.sub.6 +    30.1551   26.1216    29.7516   54.6262    29.4248   40.7879    27.6008   8.64277    27.2417   20.1564    27.1207   21.9735    26.7777   45.0824    26.0755   66.0697    25.6599   77.1097    24.3807   8.9175    23.4809   32.0249         2B.sub.4, 2B.sub.5 +, 2 EOC    22.8393   8.06774    22.1372   16.4732    19.4981   57.7003         1B.sub.1    19.3609   70.588          1B.sub.1    15.132    17.2402         1B.sub.4 +    13.8448   7.9343          1B.sub.4 +    12.2509   27.8653    12.037    27.0118    11.0766   6.61931         1B.sub.2    10.2938   98.0101         1B.sub.2    10.1364   104.811         1B.sub.2    ______________________________________

Example 80

A 22-mg (0.037-mmol) sample of (2,6-i-PrPh)DABH₂ !NiBr₂ was introducedinto a 600-mL stirred Parr® autoclave under nitrogen. The autoclave wassealed and 75 mL of dry, deaerated toluene was introduced into theautoclave via gas tight syringe through a port on the autoclave head.Then 0.6 mL of 3M poly(methylalumoxane) was added via syringe andstirring was begun. The autoclave was pressurized with propylene to 414kPa and stirred with continuous propylene feed. There was no externalcooling. The internal temperature quickly rose to 33° C. upon initialpropylene addition but gradually dropped back to 24° C. over the courseof the polymerization. After about 7 min, the propylene feed was shutoff and stirring was continued; over a total polymerization time of 1.1hr, the pressure dropped from 448 kPa to 358 kPa. The propylene wasvented and the product, a thin, honey-colored solution, was rotaryevaporated to yield 1.65 g of a very thick, brown semi-solid. This wasdissolved in chloroform and filtered through diatomaceous earth;concentration yielded 1.3 g (835 catalyst turnovers) of tacky, yellowpolypropylene rubber. Gel permeation chromatography (trichlorobenzene,135° C., polystyrene reference, results calculated as polypropyleneusinguniversal calibration theory): M_(n) =7,940; M_(w) =93,500; M_(w) /M_(n)=11.78.

Example 81

A mixture of 34 mg (0.057 mmol) of (2,6-i-PrPh)DABH₂ !NiBr₂ and 20 mLdry, deaerated toluene was magnetically-stirred under nitrogen at 5° C.in a 100-mL three-necked flask with a thermometer and a nitrogen inlettube which vented through a mineral oil bubbler. To this mixture, 0.7 mLof 3M poly(methylalumoxane) in toluene was added via syringe and theresulting deep blue-black solution was stirred for 30 min at 5° C. Tothis catalyst solution was added 35 mL of dry, deaerated cyclopentene,and the mixture was stirred and allowed to warm toroom temperature over23 hr. The blue-black mixture was filtered through alumina to removedark blue-green solids (oxidized aluminum compounds fromPMAO); thefiltrate was rotary evaporated to yield 1.2 g (310 catalyst turnovers)of clear liquid cyclopentene oligomers.

Example 82

A 20-mg (0.032 mmol) sample of (2,6-i-PrPh)DABMe₂ !NiBr₂ was placed inParr® 600-mL stirred autoclave under nitrogen. The autoclavewas sealedand 100 mL of dry, deaerated toluene and 0.6 mL of 3Mpoly(methylalumoxane) were injected into the autoclave through the headport, and mixture was stirred under nitrogen at 20° C. for 50 min. Theautoclave body was immersed in a flowing water bath and the autoclavewas then pressurized with ethylene to 2.8 MPa with stirring as theinternal temperature rose to 53° C. The autoclave was stirred at 2.8 MPa(continuous ethylene feed) for 10 min as the temperature dropped to 29°C., and the ethylene was then vented. The mixture stood at 1atm for 10min; vacuum was applied to the autoclave for a few minutes and then theautoclave was opened.

The product was a stiff, swollen polymer mass which was scraped out, cutup, and fed in portions to 500 mL methanol in a blender. The polymer wasthen boiled with a mixture of methanol (200 mL) and trifluoroacetic acid(10 mL), and finally dried under high vacuum overnight to yield 16.8 g(18,700 catalyst turnovers) of polyethylene. The polymer was somewhatheterogeneous with respect to crystallinity, as can be seen from thedifferential scanning calorimetry data below; amorphous and crystallinepieces of polymer could be picked out of the product. Crystallinepolyethylene was found in the interior of the polymer mass; amorphouspolyethylene was on the outside. The crystalline polyethylene was formedinitially when the ethylene had good access to the catalyst; as thepolymer formed limited mass transfer, the catalyst becameethylene-starvedand began to make amorphous polymer. Differentialscanning calorimetry: (crystalline piece of polymer): mp: 130° C. (150J/g); (amorphous piece of polymer): -48° C. (Tg); mp: 42° C. (3 J/g),96° C. (11 J/g). Gel permeation chromatography (trichlorobenzene, 135°C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n) =63,000; M_(w) =534,000; M_(w)/M_(n) =3.27. This example demonstrates the effect of ethylene masstransfer on the polymerization and shows that the same catalyst can makeboth amorphous and crystalline polyethylene. The bulk of the polymer wascrystalline: a film pressed at 200° C. was tough and stiff.

Example 83

A 29-mg (0.047 mmol) sample of (2,6-i-PrPh)DABMe₂ !NiBr₂ was placed inParr® 600-mL stirred autoclave under nitrogen. The autoclavewas sealedand 100 mL of dry, deaerated toluene and 0.85 mL of 3Mpoly(methylalumoxane) were injected into the autoclave through the headport. The mixture was stirred under nitrogen at 23° C. for 30 min. Theautoclave body was immersed in a flowing water bath and the autoclavewas pressurized with ethylene to 620 kPa with stirring. The internaltemperature peaked at 38° C. within 2 min. The autoclave was stirred at620 kPa (continuous ethylene feed) for 5 min as the temperaturedroppedto 32° C. The ethylene was then vented, the regulator was readjusted,and the autoclave was pressurized to 34.5 kPa (gauge) and stirred for 20min (continuous ethylene feed) as the internal temperature dropped to22° C. In the middle of this 20 min period, the ethylenefeed wastemporarily shut off for 1 min, during which time the autoclave pressuredropped from 34.5 kPa (gauge) to 13.8 kPa; the pressure was thenrestored to 34.5 kPa. After stirring 20 min at 34.5 kPa, the autoclavewasonce again pressurized to 620 kPa for 5 min; the internal temperaturerose from 22° C. to 34° C. The ethylene feed was shut off for about 30sec before venting; the autoclave pressure dropped to about 586 kPa.

The ethylene was vented; the product was a dark, thick liquid. Methanol(200 mL) was added to the autoclave and the mixture was stirred for 2hr. The polymer, swollen with toluene, had balled up on the stirrer, andthe walls and bottom of the autoclave were coated with white, fibrousrubbery polymer. The polymer was scraped out, cut up, and blended withmethanol ina blender and then stirred with fresh boiling methanol for 1hr. The white rubber was dried under high vacuum for 3 days to yield 9.6g (7270 catalyst turnovers) of rubbery polyethylene. ¹ H NMR analysis(CDCl₃): 95 methyl carbons per 1000 methylene carbons.

Differential scanning calorimetry: -51° C. (Tg); mp: 39.5° C.(4 J/g);mp: 76.4° C. (7 J/g). Gel permeation chromatography (trichlorobenzene,135° C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n) =223,000; M_(w) =487,000; M_(w)/M_(n) =2.19.

The polyethylene of Example 83 could be cast from hot chlorobenzene orpressed at 200° C. to give a strong, stretchy, hazy, transparent filmwith good recovery. It was not easily chloroform-soluble. This exampledemonstrates the use of the catalyst's ability (see Example 82) tomakeboth amorphous and crystalline polymer, and to make both types ofpolymer within the same polymer chain due to the catalyst's lowpropensityto chain transfer. With crystalline blocks (due to higherethylene pressure) on both ends and an amorphous region (due tolower-pressure, mass transfer-limited polymerization) in the center ofeach chain, this polymer is a thermoplastic elastomer.

Example 84

A Schlenk flask containing 147 mg (0.100 mmol) of { (2,6-i-PrPh)DABMe₂!PdMe(OEt₂)}BAF⁻ was cooled to -78° C., evacuated, and placed under anethylene atmosphere. Methylene chloride (100 ml) was addedto the flaskand the solution was then allowed to warm to room temperature andstirred. The reaction vessel was warm during the first several hours ofmixing and the solution became viscous. After being stirred for 17.4h,the reaction mixture was added to ˜600 mL of MeOH in order toprecipitate the polymer. Next, the MeOH was decanted off of the stickypolymer, which was then dissolved in ˜600 mL of petroleum ether. Afterbeing filtered through plugs of neutral alumina and silica gel, thesolution appeared clear and almost colorless. The solvent was thenremovedand the viscous oil (45.31 g) was dried in vacuo for severaldays: ¹ HNMR (CDCl₃, 400 MHz) δ1.24 (CH₂, CH), 0.82 (m, CH₃); Branching:˜128 CH₃ per 1000 CH₂ ; DSC: T_(g) =-67.7° C. GPC: Mn=29,000;Mw=112,000.

Example 85

Following the procedure of Example 84 { (2,6-i-PrPh)DABMe₂!PdMe(OEt₂)}BAF⁻ (164 mg, 0.112 mmol) catalyzed the polymerization ofethylene for 24 h in 50 mL of CH₂ Cl₂ to give 30.16 g of polymer as aviscous oil. ¹ H NMR (C₆ D₆) δ1.41 (CH₂, CH), 0.94 (CH₃); Branching:˜115 CH₃ per 1000 CH₂ ; GPC Analysis (THF, PMMA standards, RI Detector):M_(w) =262,000; M_(n) =121,000; PDI=2.2; DSC: T_(g) =-66.8° C.

Example 86

The procedure of Example 84 was followed using 144 mg (0.100 mmol) of {(2,6-i-PrPh)DABH₂ !PdMe(OEt₂)}BAF⁻ in 50 mL of CH₂ Cl₂ and a 24 hreaction time. Polymer (9.68 g) was obtained as a free-flowing oil. ¹ HNMR (CDCl₃, 400 MHz) δ5.36 (m, RHC═CHR'), 5.08 (br s, RR'C═CHR"), 4.67(br s, H₂ C═CRR'), 1.98 (m, allylic H), 1.26 (CH₂, CH), 0.83 (m,CH₃);Branching: ˜149 CH₃ per 1000 CH₂ ; DSC: T_(g) =-84.6° C.

Example 87

A 30-mg (0.042-mmol) sample of (2,6-i-PrPh)DABAn!NiBr₂ was placed inParr® 600-mL stirred autoclave under nitrogen. The autoclave was sealedand 150 mL of dry toluene and 0.6 mL of 3M polymethylalumoxanewereinjected into the autoclave through the head port. The autoclavebody was immersed in a flowing water bath and the mixture was stirredunder nitrogen at 20° C. for 1 hr. The autoclave was then pressurizedwith ethylene to 1.31 MPa with stirring for 5 min as the internaltemperature peaked at 30° C. The ethylene was then vented to 41.4 kPa(gauge) and the mixture was stirred and fed ethylene at 41.4 kPa for 1.5hr as the internal temperature dropped to 19° C. At the end of thistime, the autoclave was again pressurized to 1.34 MPa and stirred for7min as the internal temperature rose to 35° C.

The ethylene was vented and the autoclave was briefly evacuated; theproduct was a stiff, solvent-swollen gel. The polymer was cut up,blended with 500 mL methanol in a blender, and then stirred overnightwith 500 mL methanol containing 10 mL of 6N HCl. The stirred suspensionin methanol/HCl was then boiled for 4 hr, filtered, and dried under highvacuum overnight to yield 26.1 g (22,300 catalyst turnovers) ofpolyethylene. Differential scanning calorimetry: -49° C. (Tg); mp: 116°C. (42 J/g). The melting transition was very broad and appeared to beginaround room temperature. Although the melting point temperature ishigher in this Example than in Example 76, the area under the meltingendotherm is less in this example, implying that the polymer of thisExample is less crystalline overall, but the crystallites that do existare more ordered. This indicates that the desired block structure wasobtained. Gel permeation chromatography (trichlorobenzene, 135°C.,polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n) =123,000; M_(w) =601,000;M_(w)/M_(n) =4.87. The polyethylene of this example could be pressed at200° C. to give a strong, tough, stretchy, hazy film with partialelastic recovery. When the stretched film was plunged into boilingwater, it completely relaxed to its original dimensions.

Example 88

A 6.7-mg (0.011-mmol) sample of (2,6-i-PrPh)DABMe₂ !NiBr₂ wasmagnetically-stirred under nitrogen in a 50-mL Schlenk flask with 25 mLofdry, deaerated toluene as 0.3 mL of 3M poly(methylalumoxane) wasinjected via syringe. The mixture was stirred at 23° C. for 40 min togive adeep blue-green solution of catalyst. Dry, deaerated cyclopentene(10 mL) was injected and the mixture was stirred for 5 min. The flaskwas then pressurized with ethylene at 20.7 MPa and stirred for 22 hr.The resultingviscous solution was poured into a stirred mixture of 200mL methanol and 10 mL 6N HCl. The methanol was decanted off and replacedwith fresh methanol, and the polymer was stirred in boiling methanol for3 hr. The tough, stretchy rubber was pressed between paper towels anddried under vacuum to yield 1.0 g of poly ethylene/cyclopentene!. By ¹ HNMR analysis(CDCl₃): 100 methyl carbons per 1000 methylene carbons.Comparison of the peaks attributable to cyclopentene (0.65 ppm and 1.75ppm) with the standard polyethylene peaks (0.9 ppm and 1.3 ppm)indicates about a 10 mol % cyclopentene incorporation. This polymeryield and composition represent about 2900 catalyst turnovers.Differential scanningcalorimetry: -44° C. (Tg). Gel permeationchromatography (trichlorobenzene, 135° C., polystyrene reference,results calculated as polyethylene using universal calibration theory):M_(n) =122,000; M_(w) =241,000; M_(w) /M_(n) =1.97.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    50.9168  5.96663    46.3865  3.27366        1 cme and/or 1,3 ccmcc    40.7527  40.5963        2 eme    40.567   41.9953        1,3 eme    40.3336  45.8477        1,3 eme    37.1985  60.1003    36.6998  41.2041    36.0579  11.2879    35.607   25.169    34.4771  19.0834    34.0845  22.8886    33.1243  20.1138    32.8962  27.6778    31.8406  75.2391    30.0263  76.2755    29.6921  170.41    28.9494  18.8754    28.647   25.8032    27.4588  22.2397    27.1086  48.0806    24.3236  3.31441    22.5783  4.64411        2B.sub.5 +, 2 EOC    19.6712  43.1867        1B.sub.1    17.5546  1.41279        end group    14.3399  1.74854        1B.sub.3    13.8518  5.88699        1B.sub.4 +, 1 EOC    10.9182  2.17785        2B.sub.1    ______________________________________

Example 89

A 7.5-mg (0.013-mmol) sample of (2,6-t-BuPh)DABMe₂ !NiBr₂ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 40 mLofdry, deaerated toluene as 0.5 mL of 3M poly(methylalumoxane) wasinjected via syringe. The mixture was stirred at 23° C. for 1 hr to givea deep blue-green solution of catalyst. The flask was pressurized withethylene at 20.7 kPa (gauge) and stirred for 20 hr. The solution, whichhad become a reddish-brown suspension, was poured into a stirred mixtureof 200 mL methanol and 10 mL 6N HCl and was stirred at reflux for 1 hr.The methanol was decanted off and replaced with fresh methanol, and thewhite polymer was stirred in boiling methanol for 1 hr. The stiff,stretchy rubber was pressed between paper towels and then dried undervacuum to yield 1.25 g (3380 catalyst turnovers) of polyethylene. ¹ H-1NMR analysis (C₆ D₆): 63 methyl carbons per 1000 methylene carbons.Differential scanning calorimetry: -34° C. (Tg); mp: 44° C. (31 J/g);mp: 101° C. (23 J/g).

Example 90

A 5.5 mg (0.0066 mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂O)}SbF₆ ⁻ was allowed to stand at room temperaturein air for 24 hr. A100-mL three-neck flask with a magnetic stirrer and a gas inlet dip tubewas charged with 40 mL of reagent methylene chloride and ethylene gaswas bubbled through with stirring to saturate the solventwith ethylene.The sample of { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O)}SbF₆ ⁻ was then rinsedinto the flask with 5 mLof methylene chloride and ethylene was bubbledthrough with stirring for 5 hr. The clear yellow solution was rotaryevaporated to yield 0.20 g (1080 catalyst turnovers) of a thick yellowliquid polyethylene.

Example 91

A 600-mL stirred Parr® autoclave was sealed and flushed with nitrogen,and 100 mL of dry, deaerated toluene was introduced into the autoclaveviagas tight syringe through a port on the autoclave head. The autoclavewas purged with propylene gas to saturate the solvent with propylene.Then 45 mg (0.054 mmol) of { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O)}SbF₆ ⁻was introduced into the autoclave in the following manner: a 2.5-mL gastight syringe with a syringe valve was loaded with 45mg of {(2,6-i-PrPh)₂ DABMe₂ !PdMe (Et₂ O)}SbF₆ ⁻ under nitrogen in a glove box;then 1-2 mL of dry, deaerated methylene chloride was drawn up into thesyringe and the contents were quickly injected into the autoclavethrough a head port. This method avoids havingthe catalyst in solutionwith no stabilizing ligands.

The autoclave was pressurized with propylene to 414 MPa and stirred for2.5hr, starting with continuous propylene feed. The autoclave was cooledin a running tap water bath at 22° C. The internal temperature quicklyrose to 30° C. upon initial propylene addition but soon dropped back to22° C. After 0.5 hr, the propylene feed was shut off and stirring wascontinued. Over 2 hr, the pressure dropped from 41.4 MPa to 38.6 MPa.The propylene was then vented. The product was a thin, honey-coloredsolution. Rotary evaporation yielded 2.3 g (1010 catalyst turnovers) ofvery thick, dark-brown liquid polypropylene which was almostelastomericwhen cool. Gel permeation chromatography (trichlorobenzene, 135° C.,polystyrene reference, results calculated as polypropyleneusinguniversal calibration theory): M_(n) =8,300; M_(w) =15,300; M_(w) /M_(n)=1.84. ¹³ C NMR analysis; branching per 1000 CH₂ : total Methyls (545),Propyl (1.3), ≧Butyl and end of chain (9.2); chemical shifts. Thepolymer exhibited a glass transition temperature of -44° C. bydifferential scanning calorimetry.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    CDCl.sub.3, RT, 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    46.4978  13.2699     Methylenes    45.8683  11.9947     Methylenes    45.3639  10.959      Methylenes    45.1783  11.3339     Methylenes    44.5568  8.41708     Methylenes    44.4398  7.69019     Methylenes    44.3026  6.29108     Methylenes    44.1372  6.73541     Methylenes    43.5036  5.49837     Methylenes    42.4262  5.03113     Methylenes    41.6918  3.72552     Methylenes    39.1537  4.23147     Methines and Methylenes    38.7179  25.2596     Methines and Methylenes    37.8664  10.0979     Methines and Methylenes    37.6727  14.3755     Methines and Methylenes    37.0755  17.623      Methines and Methylenes    36.781   42.0719     Methines and Methylenes    36.559   10.0773     Methines and Methylenes    34.5495  5.34388     Methines and Methylenes    34.3195  7.48969     Methines and Methylenes    33.5488  12.6148     Methines and Methylenes    33.351   20.5271     Methines and Methylenes    32.7982  4.10612     Methines and Methylenes    32.4106  22.781      Methines and Methylenes    31.8701  5.90488     Methines and Methylenes    31.5957  10.6988     Methines and Methylenes    29.8364  44.4935     Methines and Methylenes    29.7072  103.844     Methines and Methylenes    29.3925  152.645     Methines and Methylenes    29.0293  6.71341     Methines and Methylenes    27.6089  38.7993     Methines and Methylenes    27.4193  10.3543     Methines and Methylenes    27.0763  66.8261     Methines and Methylenes    26.9552  92.859      Methines and Methylenes    26.7615  55.7233     Methines and Methylenes    26.3661  20.1674     Methines and Methylenes    24.8529  16.9056     Methine Carbon of XXVIII    23.1217  12.5439     Methine carbons of XXVIII and                         XXIX, 2B.sub.4 +, EOC    22.6779  13.0147     Methine carbons of XXVIII and                         XXIX, 2B.sub.4 +, EOC    22.5245  9.16236     Methine carbons of XXVIII and                         XXIX, 2B.sub.4 +, EOC    22.3389  77.3342     Methine carbons of XXVIII and                         XXIX, 2B.sub.4 +, EOC    21.9757  9.85242     Methine carbons of XXVIII and                         XXIX, 2B.sub.4 +, EOC    21.1405  10.0445     Methyls    20.4182  8.49663     Methyls    19.9743  25.8085     Methyls    19.825   31.4787     Methyls    19.3811  44.9986     Methyls    19.1995  31.3058     Methyls    13.8569  6.37761     Methyls    13.8004  7.67242     Methyls    137.452  22.0529     Methyls    128.675  44.6993     Methyls    127.88   43.8939     Methyls    124.959  22.4025     Methyls    122.989  3.3312      Methyls    ______________________________________

Example 92

A 600-mL stirred Parr® autoclave was sealed, flushed with nitrogen,andheated to 60° C. in a water bath. Fifty mL (48 g; 0.56 mol) of dry,deaerated methyl acrylate was introduced into the autoclave via gastight syringe through a port on the autoclave head and ethylene gas waspassed through the autoclave at a low rate to saturate the solvent withethylene before catalyst addition. Then 60 mg (0.07 mmol) of {(2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O)}SbF₆ ⁻ was introduced into theautoclave in the following manner: a 2.5-mL gas tight syringe with asyringe valve was loaded with 60 mg of { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂O)}SbF₆ ⁻ under nitrogen in a glove box; then 1 mL of dry, deaeratedmethylene chloride was drawn up into the syringe and the contents werequickly injected into the autoclave through a head port.This methodavoids having the catalyst in solution with no stabilizing ligands.

The autoclave was pressurized with ethylene to 689 kPa and continuouslyfedethylene with stirring for 4.5 hr; the internal temperature was verysteadyat 60° C. The ethylene was vented and the product, a clear yellowsolution, was rinsed out of the autoclave with chloroform, rotaryevaporated, and held under high vacuum overnight to yield 1.56 g of thinlight-brown liquid ethylene/methyl acrylate copolymer. The infraredspectrum of the product exhibited a strong ester carbonyl stretch at1740 cm⁻¹. ¹ H-1 NMR analysis (CDCl₃): 61 methyl carbons per 1000methylene carbons. Comparison of the integrals of the ester methoxy(3.67 ppm) and ester methylene (CH₂ COOMe; 2.3 ppm) peaks with theintegrals of the carbon chain methyls (0.8-0.9 ppm) and methylenes(1.2-1.3 ppm) indicated a methyl acrylate content of 16.6 mol % (37.9 wt%). This product yield and composition represent 480 ethylene turnoversand 96 methyl acrylate turnovers. ¹³ C NMR analysis; branching per 1000CH₂ : total methyls (48.3), Methyl (20.8), Ethyl (10.5), Propyl (1),Butyl (8), ≧Amyl and End of Chain (18.1), methyl acrylate (94.4);ester-bearing --CH(CH₂)_(n) CO₂ CH₃ branches as a% of total ester: n≧5(35.9), n=4 (14.3), n=1,2,3 (29.5), n=0 (20.3); chemical shifts werereferenced to the solvent: the high field carbon of1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography(tetrahydrofuran, 30°0 C., polymethylmethacrylate reference, resultscalculated as polymethylmethacrylate using universal calibrationtheory): M_(n) =3,370; M_(w) =5,450; M_(w) /M_(n) =1.62.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB 120C, 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    53.7443  2.19635    CH.sub.2 Cl.sub.2 solvent impurity    50.9115  8.84408    50.641   132.93    45.5165  7.55996    MEB.sub.0 43.8 ppm: 2 adjacent MEB.sub.0    39.6917  2.71676    39.2886  7.91933    38.1639  13.843    37.7926  26.6353    37.1666  20.6759    36.6733  8.65855    34.6256  17.6899    34.4612  16.7388    34.1429  85.624    33.9095  124.997    1EB.sub.4 +    33.676   40.0271    Contributions from EB    33.2888  11.4719    Contributions from EB    32.8644  14.4963    Contributions from EB    32.3498  17.5883    Contributions from EB    32.0475  9.83096    Contributions from EB    31.8459  30.9676    Contributions from EB    31.7079  12.7737    Contributions from EB    31.5912  13.8792    Contributions from EB    31.0873  19.6266    Contributions from EB    30.6258  10.5512    30.1324  58.6101    29.6497  169.398    29.4322  48.5318    29.1934  95.4948    27.8619  8.70181    27.4269  32.9529    26.9283  78.0563    26.5145  27.0608    26.3554  14.0683    25.4588  21.9081    2EB.sub.4 (tent)    25.3315  9.04646    2EB.sub.4 (tent)    24.9761  64.2333    2EB.sub.5 +    24.2069  10.771     BBB (beta-beta-B)    23.0451  9.50073    2B.sub.4    22.9337  6.90528    2B.sub.4    22.5518  30.0427    2B.sub.5 +, EOC    19.9842  1.87415    2B.sub.3    19.6288  17.125     1B.sub.1    19.1673  6.0427     1B.sub.1    16.7695  2.23642    14.3     --         1B.sub.3    13.7882  34.0749    1B.sub.4 +, EOC    11.0774  4.50599    1B.sub.2    10.8705  10.8817    1B.sub.2    189.989  1.04646    EB.sub.0 Carbonyl    175.687  3.33867    EB.sub.0 Carbonyl    175.406  14.4124    EB.sub.0 Carbonyl    175.22   5.43832    EB.sub.0 Carbonyl    175.061  3.53125    EB.sub.0 Carbonyl    172.859  11.2356    EB.sub.1 + Carbonyl    172.065  102.342    EB.sub.1 + Carbonyl    172.09   7.83303    EB.sub.1 + Carbonyl    170.944  3.294      EB.sub.1 + Carbonyl    ______________________________________

Example 93

A 45-mg (0.048-mmol) sample of { (2,6-i-PrPh)₂ DABAn!PdMe(Et₂ O)}SbF₆ ⁻was placed in a 600-mL Parr ® stirred autoclave under nitrogen. To thiswas added 50 mL of dry, deaerated methylene chloride, and the autoclavewas pressurized to 414 kPa with ethylene. Ethylene was continuously fedat 414 kPa with stirring at 23°-25° C. for 3 hr; then the feed was shutoff and the reaction was stirred for 12 hr more. At the end of thistime, the autoclave was under 89.6 kPa (absolute). The autoclave wasrepressurized to 345 kPa with ethylene and stirred for 2 hr more as thepressure droppedto 255 kPa, showing that the catalyst was still active;the ethylene was then vented. The brown solution in the autoclave wasrotary evaporated, taken up in chloroform, filtered through alumina toremove catalyst, and rotary evaporated and then held under high vacuumto yield 7.35 g of thick, yellow liquid polyethylene. ¹ H NMR analysis(CDCl₃): 131methyl carbons per 1000 methylene carbons. Gel permeationchromatography (trichlorobenzene, 135° C., polystyrene reference,results calculated as polyethylene using universal calibration theory):M_(n) =10,300; M_(w) =18,100; M_(w) /M_(n) =1.76.

Example 94

A 79-mg (0.085-mmol) sample of { (2,6-i-PrPh)₂ DABAn!PdMe(Et₂ O)}SbF₆ ⁻was placed in a 600-mL Parr ® stirred autoclave under nitrogen. To thiswas added 50 mL of dry, deaerated methyl acrylate,and the autoclave waspressurized to 689 kPa with ethylene. The autoclave was warmed to 50° C.and the reaction was stirred at 689 kPa for 70hr; the ethylene was thenvented. The clear yellow solution in the autoclave was filtered throughalumina to remove catalyst, rotary evaporated, and held under highvacuum to yield 0.27 g of liquid ethylene/methyl acrylate copolymer. Theinfrared spectrum or the product exhibited a strong ester carbonylstretch at 1740 cm⁻¹. ¹ H NMR analysis (CDCl₃): 70 methyl carbons per1000 methylene carbons; 13.5 mol % (32 wt %) methyl acrylate. This yieldand composition represent 12 methyl acrylate turnovers and 75 ethyleneturnovers.

Example 95

A 67-mg (0.089-mmol) of { (2,4,6-MePh)₂ DABMe₂ !PdMe(Et₂ O)}SbF₆ ⁻ wasplaced in a 200-mL glass centrifuge bottle with a magnetic stir barunder nitrogen. To this was added 40 mL of dry, deaerated methylenechloride. The bottle was immediately pressurized to 207 kPa withethylene. Ethylene was continuously fed at 207 kPa with stirring at23°-25° C. for 4 hr. After 4 hr, the ethylene feed was shut off and thereaction was stirred for 12 hr more. At the end of this time, the bottlewas under zero pressure (gauge). The brown solution was rotaryevaporated and held under high vacuum to yield 5.15 g of thick, brownliquid polyethylene. ¹ H NMR analysis (CDCl₃): 127 methyl carbons per1000 methylene carbons. Gel permeation chromatography (trichlorobenzene,135° C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n) =20,200; M_(w) =32,100; M_(w)/M_(n) =1.59.

Example 96

A 56-mg (0.066-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂C(O)CH₃)}SbF₆ ⁻ was placed in a 600-mL Parr® stirred autoclave undernitrogen. To this was added 30 mL of dry, deaeratedperfluoro(propyltetrahydrofuran). The autoclave was stirred andpressurized to 5.9 MPa with ethylene. The internal temperature peaked at29° C.; a cool water bath was placed around the autoclave body.Thereaction was stirred for 16 hr at 23° C. and 5.9 MPa and the ethylenewas then vented. The autoclave contained a light yellow granular rubber,this was scraped out of the autoclave and held under high vacuum toyield 29.0 g (15,700 catalyst turnovers) of spongy, non-tacky, rubberypolyethylene which had good elastic recovery and was very strong; it wassoluble in chloroform or chlorobenzene.

The polyethylene was amorphous at room temperature: it exhibited a glasstransition temperature of -57° C. and a melting endotherm of -16° C. (35J/g) by differential scanning calorimetry. On cooling, there was acrystallization exotherm with a maximum at 1° C. (35 J/g). Uponremelting and recooling the melting endotherm and crystallizationexotherm persisted, as did the glass transition. Dynamic mechanicalanalysis at 1 Hz showed a tan δ peak at -51° C. and a peak in the lossmodulus E" at -65° C.; dielectric analysis at 1000 Hz showed a tan dpeak at -35° C. ¹ H NMR analysis (CDCl₃): 86 methyl carbons per 1000methylene carbons. ¹³ C NMR analysis: branching per 1000 CH₂ : totalMethyls (89.3), Methyl (37.2), Ethyl (14), Propyl (6.4), Butyl (6.9),≧Am and End Of Chain(23.8); chemical shifts were referenced to thesolvent: the high field carbon of 1,2,4-trichlorobenzene (127.8 ppm).Gel permeation chromatography (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n) =137,000; M_(w) =289,000; M_(w) /M_(n) =2.10.Intrinsic viscosity (trichlorobenzene, 135° C.): 2.565 dL/g. Absolutemolecular weight averages corrected for branching: M_(n) =196,000; M_(w)=425,000; M_(w) /M_(n) =2.17. Density (determined at room temperaturewith a helium gas displacement pycnometer): 0.8546±0.0007 g/cc.

Example 97

A 49-mg (0.058 mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ C(O)CH₃}SbF₆ ⁻ was placed in a 600-mL Parr® stirred autoclave under nitrogen.To this was added 30 mL of dry, deaerated hexane. The autoclave wasstirred and pressurized to 5.9 MPa with ethylene. The internaltemperature peaked briefly at 34° C.; acool water bath was placed aroundthe autoclave body. The reaction was stirred for 16 hr at 23° C. At 14hr, the ethylene feed was shut off; the autoclave pressure dropped to5.8 MPa over 2 hr; the ethylene wasthen vented. The autoclave containeda light yellow, gooey rubber swollen with hexane, which was scraped outof the autoclave and held under high vacuum to yield 28.2 g (17,200catalyst turnovers) of spongy, non-tacky, rubbery polyethylene which hadgood elastic recovery and which was very strong.

The polyethylene was amorphous at room temperature: it exhibited a glasstransition temperature of -61° C. and a melting endotherm of -12° C. (27J/g) by differential scanning calorimetry. Dynamic mechanical analysisat 1 Hz showed a tan d peak at -52° C. and a peak in the loss modulus E"at -70° C.; dielectric analysis at 1000Hz showed a tan d peak at -37° C.¹ H NMR analysis (CDCl₃): 93 methyl carbons per 1000 methylene carbons.13C NMR analysis: branching per 1000 CH₂ : total Methyls (95.4), Methyl(33.3), Ethyl (17.2), Propyl (5.2), Butyl (10.8), Amyl (3.7), ≧Hex andEnd Of Chain (27.4); chemical shifts were referenced to the solvent: thehigh field carbon of 1,2,4-trichlorobenzene (127.8 ppm). Gel permeationchromatography (trichlorobenzene, 135° C., polystyrene reference,results calculated as polyethylene using universal calibration theory):M_(n) =149,000; M_(w) =347,000; M_(w) /M_(n) =2.33. Density (determinedat room temperature with a helium gas displacement pycnometer):0.8544±0.0007 g/cc.

Example 98

Approximately 10-mesh silica granules were dried at 200° C. andwereimpregnated with a methylene chloride solution of { (2, 6-i-PrPh)₂DABMe₂ !PdCH₂ CH₂ C(O)CH₃ }SbF₆ ⁻ to give a 10 wt % loading of thecatalyst on silica.

A 0.53-g (0.063 mmol) sample of silica gel containing 10 wt % {(2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ C(O)CH₃ }SbF₆ ⁻ was placed in a 600-mLParr® stirred autoclave undernitrogen. To this was added 40 mL of dry,deaerated hexane. The autoclave was stirred and pressurized to 5.5 MPawith ethylene; the ethylene feed was then turned off. The internaltemperature peaked briefly at 31°C. The reaction was stirred for 14 hrat 23° C. as the pressure dropped to 5.3 MPa; the ethylene was thenvented. The autoclave contained a clear, yellow, gooey rubber swollenwith hexane. The product was dissolved in 200 mL chloroform, filteredthrough glass wool, rotary evaporated, and held under high vacuum toyield 7.95 g (4500 catalyst turnovers) of gummy, rubbery polyethylene. ¹H NMR analysis (CDCl₃): 96 methyl carbons per 1000 methylene carbons.Gel permeationchromatography (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n) =6,900; M_(w) =118,000; M_(w) /M_(n) =17.08.

Example 99

A 108-mg (0.073 mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂C(O)CH₃ }BAF⁻ was placed in a 600-mL Parr® stirred autoclave undernitrogen. To this was added via syringe 75 mL of deaerated reagent grademethyl acrylate containing 100 ppm hydroquinone monomethyl ether and 100ppm of phenothiazine. The autoclave was pressurized to 5.5 MPa withethylene and was stirred at 35° C. as ethylene was continuously fed for90 hr; the ethylene was then vented. The product consisted of a swollenclear foam wrapped around the impeller;40 mL of unreacted methylacrylate was poured off the polymer. The polymer was stripped off theimpeller and was held under high vacuum to yield 38.2g of clear,grayish, somewhat-tacky rubber. ¹ H NMR analysis (CDCl₃): 99 methylcarbons per 1000 methylene carbons. Comparison of the integrals of theester methoxy (3.67 ppm) and ester methylene (CH₂ COOMe; 2.30 ppm) peakswith the integrals of the carbon chain methyls (0.8-0.9 ppm) andmethylenes (1.2-1.3 ppm) indicated a methyl acrylate content of 0.9 mol% (2.6 wt %). This product yield and composition represent 18,400ethylene turnovers and 158 methyl acrylate turnovers. ¹³ C NMR analysis:branching per 1000 CH₂ : total Methyls (105.7), Methyl (36.3), Ethyl(22), Propyl (4.9), Butyl (10.6), Amyl (4), ≧Hex and End Of Chain(27.8), methyl acrylate (3.4); ester-bearing --CH(CH2)_(n) CO2CH3branches as a % of total ester: n≧5 (40.6), n=1,2,3 (2.7), n=0 (56.7);chemical shifts were referenced to the solvent: the high field carbon of1,2,4-trichlorobenzene(127.8 ppm). Gel permeation chromatography(tetrahydrofuran, 30° C.,polymethylmethacrylate reference, resultscalculated as polymethylmethacrylate using universal calibrationtheory): M_(n) =151,000; M_(w) =272,000; M_(w) /M_(n) =1.81.

Example 100

A 62-mg (0.074-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O)}SbF₆⁻ was placed in a 600-mL Parr® stirredautoclave under nitrogen with 200mL of deaerated aqueous 10% (v/v) n-butanol. The autoclave waspressurized to 2.8 MPa with ethylene and was stirred for 16 hr. Theethylene was vented and the polymer suspension was filtered. The productconsisted of a fine gray powdery polymer along with some largerparticles of sticky black polymer; the polymer was washed withacetoneand dried to yield 0.60 g (290 catalyst turnovers) of polyethylene.Thegray polyethylene powder was insoluble in chloroform at RT; it wassoluble in hot tetrachloroethane, but formed a gel on cooling to RT. ₁ HNMR analysis (tetrachloroethane-d₂ ; 100° C.): 43 methyl carbons per1000 methylene carbons. Differential scanning calorimetry exhibited amelting point at 89° C. (78 J/g) with a shoulder at 70° C.; there was noapparent glass transition.

Example 101

A 78-mg (0.053-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ C(O)CH₃}BAF⁻ was placed in a 600-mL Parr® stirred autoclave under nitrogen. Tothis was added 40 mL of dry, deaerated t-butyl acrylate containing 100ppm hydroquinone monomethyl ether. The autoclave was pressurized withethylene to 2.8 MPa and was stirred and heated at 35° C. as ethylene wascontinuously fed at 2.8 MPa for 24hr; the ethylene was then vented. Theproduct consisted of a yellow, gooey polymer which was dried under highvacuum to yield 6.1 g of clear, yellow,rubbery ethylene/t-butyl acrylatecopolymer which was quite tacky. ¹ HNMR analysis (CDCl₃): 102 methylcarbons per 1000 methylene carbons. Comparison of the integral of theester t-butoxy (1.44 ppm) peak with the integrals of the carbon chainmethyls (0.8-0.9 ppm) and methylenes (1.2-1.3 ppm) indicated a t-butylacrylate content of 0.7 mol % (3.3 wt %). This yield and compositionrepresent 3960 ethylene turnovers and 30 t-butyl acrylate turnovers. Gelpermeation chromatography (tetrahydrofuran, 30° C.,polymethylmethacrylate reference, resultscalculated aspolymethylmethacrylate using universal calibration theory): M_(n)=112,000; M_(w) =179,000; M_(w) /M_(n) =1.60.

Example 102

A 19-mg (0.022-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ C(O)CH₃}SbF₆ ⁻ was placed in a 600-mL Parr® stirred autoclave under nitrogen.The autoclave was pressurized to 5.2 MPawith ethylene and was stirredfor 2 hr; the ethylene feed was then shut off. The autoclave was stirredfor 16 hr more as the ethylene pressure dropped to 5.0 MPa; the ethylenewas then vented. The autoclave contained a light yellow, granular spongerubber growing all over the walls and headof the autoclave; this wasscraped out to yield 13.4 g (21,800 catalyst turnovers) of spongy,non-tacky, rubbery polyethylene which was very strong and elastic. ¹ HNMR analysis (CDCl₃): 90 methyl carbons per 1000 methylene carbons.

Differential scanning calorimetry exhibited a glass transition at -50°C. Gel permeation chromatography (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n) =175,000; M_(w) =476,000; M_(w) /M_(n) =2.72.

Example 103

A 70-mg (0.047-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ C(O)CH₃}BAF⁻ was placed in a 600-mL Parr® stirred autoclave under nitrogen. Tothis was added 70 mL of deaerated reagent grade methyl acrylatecontaining 100 ppm each hydroquinone monomethyl ether and phenothiazineand 0.7 mL (1 wt %; 4.7 mol %) deaerated, deionized water. The autoclaveWas stirred at 35° C. as ethylene was continuously fed at 4.8 MPa for 16hr; the ethylene was then vented. The product consisted of a clearsolution. Rotary evaporation yielded 1.46g of ethylene/methyl acrylatecopolymer as a clear oil. The infrared spectrum of the product exhibiteda strong ester carbonyl stretch at 1740 cm¹. ¹ H NMR analysis (CDCl₃):118 methyl carbons per 1000 methylene carbons. Comparison of theintegrals of the ester methoxy (3.67 ppm) and ester methylene (CH₂COOMe; 2.30 ppm) peaks with the integrals of the carbon chain methyls(0.8-0.9 ppm) and methylenes (1.2-1.3 ppm) indicated a methyl acrylatecontent of 0.7 mol % (2.2 wt %).This product yield and compositionrepresent 1090 ethylene turnovers and 8 methyl acrylate turnovers. Gelpermeation chromatography (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n) =362; M_(w) =908; M_(w) /M_(n) =2.51.

Example 104

A 53-mg (0.036-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ C(O)CH₃}BAF⁻ was placed in a 600-mL Parr® stirred autoclave under nitrogen. Tothis was added 100 mL of dry, deaerated methylene chloride. Theautoclave was immersed in a cool water bath and stirred as it waspressurized to 4.8 MPa with ethylene. Ethylene was continuously fed withstirring at 4.8 MPa and 23° C. for 23 hr; theethylene then was vented.The product consisted of a clear rubber, slightlyswollen with methylenechloride. The polymer was dried under high vacuum atroom temperature toyield 34.5 g (34,100 catalyst turnovers) of clear rubbery polyethylene.¹ H NMR analysis (CDCl₃): 110 methyl carbons per 1000 methylene carbons.Gel permeation chromatography (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n) =243,000; M_(w) =676,000; M_(w) /M_(n) =2.78.

Example 104A

A 83-mg (0.056-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ C(O)CH₃}BAF⁻ was placed in a 600-mL Parr® stirred autoclave under nitrogen. Tothis was added 70 mL of dry, deaerated, ethanol-free chloroform. Theautoclave was immersed in a cool water bath and stirred as it waspressurized to 4.7 MPa with ethylene. Ethylene was continuously fed withstirring at 4.7 MPa and 23° C. for 21 hr; theethylene then was vented.The product consisted of a pink, rubbery, foamed polyethylene, slightlyswollen with chloroform. The polymer was dried under vacuum at 40° C. toyield 70.2 g (44,400 catalyst turnovers) of pink, rubbery polyethylenewhich was slightly tacky. ¹ H NMR analysis (CDCl₃): 111 methyl carbonsper 1000 methylene carbons. Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n) =213,000; M_(w)=728,000; M_(w) /M_(n) =3.41.

Example 105

A 44-mg (0.052-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ C(O)CH₃}SbF₆ ⁻ was magnetically stirred under nitrogen in a 50-mL Schlenk flaskwith 20 mL of dry, deaerated methylene chloride. To this was added 5 mL(5.25 g; 73 mmol) of freshly distilled acrylic acid (contains a few ppmof phenothiazine as a radical polymerization inhibitor) via syringe andthe mixture was immediately pressurized with ethylene at 5.52 kPa andstirred for 40 hr. The dark yellow solution was rotary evaporated andthe residue was stirred with 50 mL water for 15 min to extract anyacrylic acid homopolymer. The water wasdrawn off with a pipette androtary evaporated to yield 50 mg of dark residue. The polymer which hadbeen water-extracted was heated under high vacuum to yield 1.30 g ofethylene/acrylic acid copolymer as a dark brown oil. The infraredspectrum showed strong COOH absorbances at 3400-2500 andat 1705 cm⁻¹, aswell as strong methylene absorbances at 3000-2900 and1470 cm⁻¹.

A 0.2-g sample of the ethylene/acrylic acid copolymer was treated withdiazomethane in ether to esterify the COOH groups and produce anethylene/methyl acrylate copolymer. The infrared spectrum of theesterified copolymer showed a strong ester carbonyl absorbance at 1750cm⁻¹ ; the COOH absorbances were gone. ¹ H NMR analysis (CDCl₃): 87methyl carbons per 1000 methylene carbons. Comparison of the integralsof the ester methoxy (3.67 ppm) and ester methylene (CH₂ COOMe; 2.30ppm) peaks with the integrals of the carbon chain methyls (0.8-0.9 ppm)and methylenes (1.2-1.3 ppm) indicated a methyl acrylate content of 5.3mol % (14.7 wt % methyl acrylate =>12.3 wt % acrylic acid in theoriginal copolymer). This product yield and composition represent 780ethylene turnovers and 43 acrylic acid turnovers. Gel permeationchromatography (tetrahydrofuran, 30° C., polymethylmethacrylatereference, results calculated as polymethylmethacrylate using universalcalibration theory): M_(n) =25,000; M_(w) =42,800; M_(w) /M_(n) =1.71.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    CDCl.sub.3, 0.05M CrAcAc    Freq ppm  Intensity    ______________________________________    51.0145   24.9141    45.434    1.11477         MEB.sub.0    38.8925   2.29147    38.5156   6.51271    37.3899   10.7484    37.0713   17.3903    36.7634   17.6341    36.4182   3.57537    36.2961   6.0822    34.459    2.158    34.0289   9.49713    33.7369   34.4456    33.3705   49.2646    32.8926   18.2918    32.3935   10.5014    32.0271   3.5697          3B.sub.5    31.5705   30.6837         3B.sub.6 +, 3 EOC    31.1723   1.54526    29.813    46.4503    29.3511   117.987    29.1387   21.034    28.9953   30.603    28.613    7.18386    27.2007   8.02265    26.744    23.8731    26.3777   46.8498    26.006    5.42389    25.5547   8.13592    25.0609   5.46013         2 EB.sub.4 (tentative)    24.9175   2.30355         2 EB.sub.4 (tentative)    24.6042   15.7434         2 EB.sub.5 +    23.7547   2.78914    23.3777   5.63727    22.7936   8.07071         2B.sub.4    22.6768   3.78032         2B.sub.4    22.3211   33.1603         2B.sub.5 +, 2 EOC    19.3477   15.4369         1B.sub.1    18.8645   5.97477         1B.sub.1    14.1814   1.99297         1B.sub.3    13.7407   38.5361         1B.sub.4 +, 1 EOC    11.0274   6.19758         1B.sub.2    10.5124   10.4707         1B.sub.2    176.567   9.61122         EB.sub.0 carbonyl    174.05    9.03673         EB.sub.1 + carbonyl    173.779   85.021          EB.sub.1 + carbonyl    ______________________________________

Example 106

A 25-mg (0.029-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ C(O)CH₃}SbF₆ ⁻ was magnetically stirred under 55.2kPa of ethylene in a 50-mLSchlenk flask with 20 mL of dry methylene chloride and 5 mL (4.5 g; 39mmol) of methyl 4-pentenoate for 40 hr at room temperature. The yellowsolution was rotary evaporated to yield 3.41 g of ethylene/methyl4-pentenoate copolymer as a yellow oil. The infrared spectrum of thecopolymer showed a strong ester carbonyl absorbance at 1750 cm⁻¹. ¹ HNMR analysis (CDCl₃): 84 methyl carbons per 1000 methylene carbons.Comparison of the integrals of the ester methoxy (3.67 ppm) and estermethylene (CH₂ COOMe; 2.30 ppm) peaks with the integrals of the carbonchain methyls (0.8-0.9 ppm) and methylenes (1.2-1.3 ppm) indicated amethyl 4-pentenoate content of 6 mol % (20 wt %). This yield andcomposition represent about 3400 ethylene turnovers and200 methyl4-pentenoate turnovers. ¹³ C NMR quantitative analysis: branching per1000 CH₂ : total Methyls (93.3), Methyl (37.7), Ethyl(18.7), Propyl (2),Butyl (8.6), ≧Am and end of chains (26.6), ≧Bu and end of chains (34.8);ester-bearing branches --CH(CH₂)_(n) CO₂ CH₃ as a % of total ester: n≧5(38.9), n=4 (8.3), n=1,2,3 (46.8), n=0 (6); chemical shifts werereferenced to the solvent: chloroform-d₁ (77 ppm). Gel permeationchromatography (tetrahydrofuran, 30° C., polymethylmethacrylatereference, results calculated as polymethylmethacrylate using universalcalibration theory): M_(n) =32,400; M_(w) =52,500; M_(w) /M_(n) =1.62.

Example 107

A 21-mg (0.025-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ C(O)CH₃}SbF₆ ⁻ was magnetically stirred under nitrogen in a 50-mL Schlenk flaskwith 5 mL of dry methylene chloride and 5 mL (4.5 g; 39 mmol) of methyl4-pentenoate for 74 hr. The yellow solution was rotary evaporated toyield 0.09 g of a yellow oil, poly methyl 4-pentenoate!. The infraredspectrum showed a strong ester carbonyl absorbance at 1750 cm⁻¹. The ¹ HNMR (CDCl₃) spectrum showed olefinic protons at 5.4-5.5 ppm; comparingthe olefin integral with the integral of the ester methoxy at 3.67 ppmindicates an average degree of polymerization of 4 to 5. This exampledemonstrates the ability of this catalyst to homopolymerize alphaolefins bearing polar functional groups not conjugated to thecarbon-carbon double bond.

Example 108

A 53-mg (0.063-mmol) sample of { (2,6-i-PrPh)₂ DADMe₂ !PdCH₂CH₂ C(O)CH₃}SbF₆ ⁻ was placed in a 600-mL Parr® stirred autoclave under nitrogen.To this was added 25 mL of dry, deaerated toluene and 25 mL (26 g; 0.36mol) of freshly distilled acrylic acid containing about 100 ppmphenothiazine. The autoclave was pressurizedto 2.1 MPa with ethylene andwas stirred for 68 hr at 23° C.; the ethylene was then vented. Theautoclave contained a colorless, hazy solution. The solution was rotaryevaporated and the concentrate was takenup in 50 mL of chloroform,filtered through diatomaceous earth, rotary evaporated, and then heldunder high vacuum to yield 2.23 g of light brown, very viscous liquidethylene/acrylic acid copolymer. The infrared spectrum showed strongCOOH absorbances at 3400-2500 and at 1705 cm⁻¹, as well as strongmethylene absorbances at 3000-2900 and 1470 cm⁻¹.

A 0.3-g sample of the ethylene/acrylic acid copolymer was treated withdiazomethane in ether to esterify the COOH groups and produce anethylene/methyl acrylate copolymer. The infrared spectrum showed astrong ester carbonyl absorbance at 1750 cm⁻¹ ; the COOH absorbanceswere gone. ¹ H NMR analysis (CDCl₃): 96 methyl carbons per 1000methylene carbons. Comparison of the integrals of the ester methoxy(3.67 ppm) and ester methylene (CH₂ COOMe; 2.30 ppm) peaks with theintegrals of the carbon chain methyls (0.8-0.9 ppm) and methylenes(1.2-1.3 ppm) indicated a methyl acrylate content of 1.8 mol % (5.4 wt %methyl acrylate =>4.5 wt % acrylic acid in the original copolymer). Thisproduct yield and composition represent 1200 ethylene turnovers and 22acrylic acid turnovers. Gel permeation chromatography (trichlorobenzene,135° C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n) =5,330; M_(w) =15,000; M_(w) /M_(n)=2.82.

Example 109

A 600-mL stirred Parr® autoclave was sealed and flushed with nitrogen.Fifty mL (48 g; 0.56 mol) of dry, deaerated methyl acrylate wasintroducedinto the autoclave via gas tight syringe through a port on theautoclave head. Then 60 mg (0.07 mmol) of { (2,6-i-PrPh)₂ DABMe₂!PdMe(Et₂ O)}BAF⁻ was introduced into the autoclave in the followingmanner: a 2.5-mL gas tight syringe with a syringe valve was loaded with60 mg of { (2,6-i-PrPh)₂ DABMe₂ !PdMe (Et₂ O)}BAF⁻ under nitrogen in aglove box; then 1 mL of dry, deaerated methylene chloride was drawn upinto the syringe and the contents were quickly injected into theautoclave through a head port. This method avoids having the catalyst insolution with no stabilizing ligands.

The autoclave body was immersed in a running tap water bath; theinternal temperature was very steady at 22° C. The autoclave waspressurizedwith ethylene to 2.8 MPa and continuously fed ethylene withstirring for 4.5 hr. The ethylene was then vented and the product, amixture of methyl acrylate and yellow gooey polymer, was rinsed out ofthe autoclave with chloroform, rotary evaporated, and held under highvacuum overnight to yield 4.2 g of thick, light-brown liquidethylene/methyl acrylate copolymer. The infrared spectrum of the productexhibited a strong ester carbonyl stretch at 1740 cm⁻¹. ¹ H NMR analysis(CDCl₃): 82methyl carbons per 1000 methylene carbons. Comparison of theintegrals of the ester methoxy (3.67 ppm) and ester methylene (CH₂COOMe; 2.30 ppm) peaks with the integrals of the carbon chain methyls(0.8-0.9 ppm) and methylenes (1.2-1.3 ppm) indicated a methyl acrylatecontent of 1.5 mol % (4.4 wt %). This product yield and compositionrepresent 2000 ethylene turnovers and 31 methyl acrylate turnovers. ¹³ CNMR analysis: branching per 1000 CH₂ : total Methyls (84.6), Methyl(28.7), Ethyl (15.5), Propyl (3.3), Butyl (8.2), ≧Hex and End Of Chain(23.9), methyl acrylate (13.9). Ester-bearing --CH(CH2)_(n)CO2CH3branches as a % of total ester: n≧5 (34.4), n=4 (6.2), n=1,2,3(13),n=0 (46.4). Mole %: ethylene (97.6), methyl acrylate (2.4);chemical shiftswere referenced to the solvent: the high field carbon of1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography(tetrahydrofuran, 30° C., polymethylmethacrylate reference,resultscalculated as polymethylmethacrylate using universal calibrationtheory): M_(n) =22,000; M_(w) =45,500; M_(w) /M_(n) =2.07.

A mixture of 1.45 g of this ethylene/methyl acrylate copolymer, 20 mLdioxane, 2 mL water, and 1 mL of 50% aqueous NaOH was magneticallystirredat reflux under nitrogen for 4.5 hr. The liquid was then decantedaway fromthe swollen polymer and the polymer was stirred several hourswith three changes of boiling water. The polymer was filtered, washedwith water and methanol, and dried under vacuum (80° C./nitrogen purge)to yield 1.2 g soft of ionomer rubber, insoluble in hot chloroform. TheFTIR-ATR spectrum of a pressed film (pressed at 125° C./6.9 MPa) showeda strong ionomer peak at 1570 cm⁻¹ and virtually no ester carbonyl at1750 cm⁻¹. The pressed film was a soft, slightly tacky rubber with abouta 50% elongation to break. This example demonstrates the preparationofan ionomer from this ethylene/methyl acrylate polymer.

Example 110

The complex (2,6-i-PrPh)₂ DABMe₂ !PdMeCl (0.020 g, 0.036 mmol) wasweighed into a vial and dissolved in 6 ml CH₂ Cl₂. NaBAF (0.032 g, 0.036mmol) was rinsed into the stirring mixture with 4 ml of CH₂ Cl₂. Therewas an immediate color change from orange to yellow. The solution wasstirred under 6.2 MPa ethylene in a Fisher Portertube with temperaturecontrol at 19° C. The internal temperature rose to 22° C. during thefirst 15 minutes. The temperature controller was raised to 30° C. After35 minutes, the reaction was consuming ethylene slowly. After a totalreaction time of about 20 h, there was no longer detectable ethyleneconsumption, but the liquid level in the tube was noticeably higher.Workup by addition to excess MeOH gave a viscous liquid precipitate. Theprecipitate was redissolved in CH₂ Cl₂, filtered through a 0.5 micronPTFE filter and reprecipitated by addition to excess MeOH to give 7.208g dark brown viscous oil (7180 equivalents of ethylene per Pd). ¹ H NMR(CDCl₃) 0.8-1.0 (m, CH₃); 1.0-1.5 (m, CH and CH₂). Integration allowscalculation ofbranching: 118 methyl carbons per 1000 methylene carbons.GPC in THF vs. PMMA standard: M_(n) =12,700, M_(w) =28,800, M_(w) /M_(n)=2.26.

Example 111

The solid complex { (2,6-i-PrPh)₂ DABMe2!PdMe(Et₂ O)}SbF₆ ⁻ (0.080 g,0.096 mmol) was placed in a Schlenk flask which was evacuated andrefilled with ethylene twice. Under one atm of ethylene, black spotsformed in the center of the solid complex and grew outward as ethylenewas polymerized in the solid state and the resulting exotherm destroyedthe complex. Solid continued to form on the solid catalyst that had notbeen destroyed by the exotherm, and the next day theflask containedconsiderable solid and the reaction was still slowly consuming ethylene.The ethylene was disconnected and 1.808 g of light gray elastic solidwas removed from the flask (644 equivalents ethylene per Pd). The ¹ HNMR in CDCl₃ was similar to example 110 with 101 methyl carbons per 1000methylene carbons. Differential Scanning Calorimetry (DSC): first heat25° to 150° C., 15° C./min, no events; second heat -150° to 150° C.,T_(g) =-53° C. with an endothermic peak centered at -20 C.; third heat-150° to 275° C., T_(g) =-51° C. with an endothermic peak centered at-20° C. GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as linear polyethylene using universal calibration theory):M_(n) =13,000 M_(w) =313,000 M_(w) /M_(n) =24.

Example 112

The complex { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O)}SbF₆ ⁻ (0.084 g, 0.100mmol) was loaded into a Schlenk flask in the drybox followed by 40 ml ofdry dioxane. The septum-capped flask was connected to a Schlenk line andthe flask was then briefly evacuated and refilled with ethylene. Thelight orange mixture was stirred under an ethylene atmosphere atslightly above 1 atm by using a mercury bubbler. There was rapid uptakeof ethylene. A room temperature water bath was usedto control thetemperature of the reaction. After 20 h, the reaction was worked up byremoving the solvent in vacuo to give 10.9 g of a highly viscous fluid(3870 equivalents of ethylene per Pd). Dioxane is a solvent for the Pdcomplex and a non-solvent for the polymer product. ¹ H NMR(CDCl₃)0.8-1.0 (m, CH₃); 1.0-1.5 (m, CH and CH₂). Integration allowscalculation of branching: 100 methyl carbons per 1000 methylene carbons.GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as linear polyethylene using universal calibration theory):Partially resolved trimodal distribution with M_(n) =16300, M_(w)=151000 M_(w) /M_(n) =9.25. DSC (second heat, -150° C. to 150° C., 15°C./min) T_(g) =-63°C., endothermic peak centered at -30° C.

Example 113

Polymerization of ethylene was carried out according to example 112,using pentane as solvent. Pentane is a non-solvent for the Pd complexand a solvent for the polymer product. The reaction gave 7.47 g of darkhighly viscous fluid (2664 equivalents of ethylene per Pd). ¹ H NMRanalysis(CDCl₃): 126 methyl carbons per 1000 methylene carbons. ¹³ C NMRanalysis, branching per 1000 CH₂ : Total methyls (128.8), Methyl (37.8),Ethyl (27.2), Propyl (3.5), Butyl (14.5), Amyl (2.5), ≧Hexyl and end ofchain (44.7), average number of carbon atoms for ≧Hexyl branches=16.6(calculated from intrinsic viscosity and GPC molecular weight data).Quantitation of the --CH₂ CH(CH₃)CH₂ CH₃ structure per 1000 CH₂ 's: 8.3.These side chains are counted as a Methyl branch and an Ethyl branch inthe quantitative branching analysis. GPC (trichlorobenzene, 135° C.,polystyrene reference, results calculated as linear polyethylene usinguniversal calibration theory): M_(n) =9,800, M_(w) =16,100, M_(w) /M_(n)=1.64. Intrinsic viscosity (trichlorobenzene, 135° C.)=0.125 g/dL.Absolute molecular weights calculated by GPC (trichlorobenzene, 135° C.,polystyrene reference, corrected for branching using measured intrinsicviscosity): M_(n) =34,900, M_(w) =58,800, M_(w) /M_(n) =1.68. DSC(second heat, -150° C. to 150° C., 15° C./min) T_(g) =-71° C.,endothermic peak centered at -43° C.

Example 114

Polymerization of ethylene was carried out according to example 112,using distilled degassed water as the medium. Water is a non-solvent forboth the Pd complex and the polymer product. The mixture was worked upby decanting the water from the product which was then dried in vacuo togive0.427 g of dark sticky solid (152 equivalents of ethylene per Pd). ¹HNMR analysis (CDCl₃): 97 methyl carbons per 1000 methylene carbons. GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aslinear polyethylene using universal calibration theory): M_(n) =25,100,M_(w) =208,000, M_(w) /M_(n) =8.31.

Example 115

Polymerization of ethylene was carried out according to example 112,using 2-ethylhexanol as the solvent. The Pd complex is sparingly solublein thissolvent and the polymer product is insoluble. The polymer productformed small dark particles of high viscosity liquid suspended in the2-ethylhexanol. The solvent was decanted and the polymer was dissolvedin CHCl₃ and reprecipitated by addition of excess MeOH. The solvent wasdecanted, and the reprecipitated polymer was dried in vacuo to give 1.66gof a dark highly viscous fluid (591 equivalents of ethylene per Pd). ¹HNMR analysis (CDCl₃): 122 methyl carbons per 1000 methylene carbons.GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aslinear polyethylene using universal calibration theory): M_(n) =7,890,M_(w) =21,600, M_(w) /M_(n) =2.74.

Example 116

The solid complex { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O)}SbF₆ ⁻ (0.084 g,0.100 mmol) was loaded into a Schlenk flask in the drybox. The flask wasconnected to a Schlenk line under 1 atm of ethylene, and cooled to -78°C. Solvent, (CH₂ Cl₂, 40 ml)was added by syringe and after equilibratingat -78° C. under ethylene, the mixture was warmed to room temperatureunder ethylene. The mixture was stirred under an ethylene atmosphere atslightly above 1 atm by using a mercury bubbler. There was rapid uptakeof ethylene. A room temperature water bath was used to control thetemperature of the reaction. After 24 h, the reaction was worked up byremoving the solvent in vacuo to give 24.5 g of a highly viscous fluid(8730 equivalents of ethylene per Pd). CH₂ Cl₂ is a good solvent forboth the Pd complex and the polymer product. The polymer was dissolvedin CH₂ Cl₂, and reprecipitated by addition to excess MeOH in a taredflask. The solvent was decanted, and the reprecipitated polymer wasdried in vacuo to give 21.3 g of a dark highly viscous fluid. ¹ H NMRanalysis(CDCl₃): 105 methyl carbons per 1000 methylene carbons. C-13 NMRanalysis, branching per 1000 CH₂ : Total methyls (118.6), Methyl (36.2),Ethyl (25.9), Propyl (2.9), Butyl (11.9), Amyl (1.7), ≧Hexyl and end ofchains (34.4), average number of carbon atoms for ≧Hexyl branches=22.5(calculated from intrinsic viscosity and GPC molecular weight data).Quantitation of the --CH₂ CH(CH₃)CH₂ CH₃ structure per 1000 CH₂ 's: 8.1.These side chains also counted as a Methyl branch and an Ethyl branch inthe quantitative branching analysis. GPC (trichlorobenzene, 135° C.,polystyrene reference, results calculated as linear polyethylene usinguniversal calibration theory): M_(n) =25,800, M_(w) =45,900, M_(w)/M_(n) =1.78. Intrinsic viscosity (trichlorobenzene, 135° C.)=0.24 g/dL.Absolute molecular weights calculated by GPC (trichlorobenzene, 135° C.,polystyrene reference, corrected for branching using measured intrinsicviscosity): M_(n) =104,000, M_(w) =188,000, M_(w) /M_(n) =1.81.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.06M CrAcAc    Freq ppm  Intensity    ______________________________________    39.7233   5.12305    39.318    17.6892       MB.sub.2    38.2022   17.9361       MB.sub.3 +    37.8369   32.3419       MB.sub.3 +    37.2469   43.1136       αB.sub.1, 3B.sub.3    36.8335   10.1653       αB.sub.1, 3B.sub.3    36.7452   14.674        αB.sub.1, 3B.sub.3    34.9592   10.3554       αγ+B, (4B.sub.4, 5B.sub.5, etc.)    34.6702   24.015        αγ+B, (4B.sub.4, 5B.sub.5, etc.)    34.5257   39.9342       αγ+B, (4B.sub.4, 5B.sub.5, etc.)    34.2006   109.158       αγ+B, (4B.sub.4, 5B.sub.5, etc.)    33.723    36.1658       αγ+B, (4B.sub.4, 5B.sub.5, etc.)    33.3136   12.0398       MB.sub.1    32.9323   20.7242       MB.sub.1    32.4266   6.47794       3B.sub.5    31.9409   96.9874       3B.sub.6 +, 3 EOC    31.359    15.2429       γ+γ+B, 3B.sub.4    31.0981   19.2981       γ+γ+B, 3B.sub.4    30.6606   15.8689       γ+γ+B, 3B.sub.4    30.2271   96.7986       γ+γ+B, 3B.sub.4    30.1188   54.949        γ+γ+B, 3B.sub.4    29.7455   307.576       γ+γ+B, 3B.sub.4    29.5809   36.2391       γ+γ+B, 3B.sub.4    29.3361   79.3542       γ+γ+B, 3B.sub.4    29.2157   23.0783       γ+γ+B, 3B.sub.4    27.6424   24.2024       βγ+B, 2B.sub.2, (4B.sub.5, etc.)    27.526    29.8995       βγ+B, 2B.sub.2, (4B.sub.5, etc.)    27.3534   23.1626       βγ+B, 2B.sub.2, (4B.sub.5, etc.)    27.1607   70.8066       βγ+B, 2B.sub.2, (4B.sub.5, etc.)    27.0042   109.892       βγ+B, 2B.sub.2, (4B.sub.5, etc.)    26.5908   7.13232       βγ+B, 2B.sub.2, (4B.sub.5, etc.)    26.3941   23.945        βγ+B, 2B.sub.2, (4B.sub.5, etc.)    25.9446   4.45077       βγ+B, 2B.sub.2, (4B.sub.5, etc.)    24.4034   9.52585       ββB    24.2428   11.1161       ββB    23.1391   21.2608       2B.sub.4    23.0227   11.2909       2B.sub.4    22.6494   103.069       2B.sub.5 +, 2 EOC    20.0526   5.13224       2B.sub.3    19.7355   37.8832       1B.sub.1    19.2017   14.8043       1B.sub.1, Structure XXVII    14.4175   4.50604       1B.sub.3    13.9118   116.163       1B.sub.4 +, 1 EOC    11.1986   18.5867       1B.sub.2, Structure XXVII    10.9617   32.3855       1B.sub.2    ______________________________________

Example 117

Polymerization of ethylene was carried out according to example 116, ata reaction temperature of 0° C. and reaction time of several hours. Thepolymer product formed a separate fluid phase on the top of the mixture.The reaction was quenched by adding 2 ml acrylonitrile. The product wasmoderately viscous fluid, 4.5 g (1600 equivalents of ethylene per Pd). ¹H NMR analysis (CDCl₃): 108 methyl carbons per 1000 methylene carbons.¹³ C NMR analysis, branching per 1000 CH₂ : Total methyls (115.7),Methyl (35.7), Ethyl (24.7), Propyl (2.6), Butyl (11.2), Amyl (3.2),≧Hexyl and end of chain (37.1). Quantitation ofthe --CH₂ CH(CH₃)CH₂ CH₃structure per 1000 CH₂ 's: 7.0. These side chains are counted as aMethyl branch and an Ethyl branch in the quantitative branchinganalysis. GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as linear polyethylene using universal calibration theory:M_(n) =15,200, M_(w) =23,700, M_(w) /M_(n) =1.56.

Example 118

The Pd complex { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻(0.084 g, 0.100 mmol) was loaded into a Schlenk flask in the drybox, and40 ml of FC-75 was added. The septum-capped flask was connected to aSchlenk line and the flask was thenbriefly evacuated and refilled withethylene from the Schlenk line. The mixture was stirred under anethylene atmosphere at slightly above 1 atm by using a mercury bubbler.Both the Pd initiator and the polymer are insoluble in FC-75. After 15days, the reaction flask contained a large amount of gray elastic solid.The FC-75 was decanted, and the solid polymer was then dissolved inCHCl₃ and precipitated by addition of the solution to excess MeOH. Thepolymer was dried in vacuo, and then dissolved in o-dichlorobenzene at100° C. The hot solution was filtered through a 10 μm PTFE filter. Thefiltered polymer solution wasshaken in a separatory funnel withconcentrated sulfuric acid, followed by distilled water, followed by 5%NaHCO₃ solution, followed by two water washes. The polymer appeared tobe a milky suspension in the organiclayer during this treatment. Afterwashing, the polymer was precipitated byaddition to excess MeOH in ablender and dried at room temperature in vacuoto give 19.6 g light grayelastic polymer fluff (6980 equivalents of ethylene per Pd). ¹ H NMRanalysis (CDCl₃): 112 methyl carbons per 1000 methylene carbons. ¹³ CNMR analysis, branching per 1000 CH₂ : Total methyls (114.2), Methyl(42.1), Ethyl (24.8), Propyl (5.1), Butyl (10.2), Amyl (4), ≧Hexyl andend of chain (30.3), average number of carbon atoms for ≧Hexylbranches=14.4 (calculatedfrom intrinsic viscosity and GPC molecularweight data). GPC (trichlorobenzene, 135° C., polystyrene reference,results calculated as linear polyethylene using universal calibrationtheory: M_(n) =110,000, M_(w) =265,000, M_(w) /M_(n) =2.40. Intrinsicviscosity (trichlorobenzene, 135° C.)=1.75 g/dL. Absolutemolecularweights calculated by GPC (trichlorobenzene, 135° C.,polystyrene reference, corrected for branching using measured intrinsicviscosity): M_(n) =214,000, M_(w) =53,000, M_(w) /M_(n) =2.51.

Example 119

Polymerization of ethylene was carried out according to example 112,using the complex { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂C(O)OCH₃ }SbF₆ ⁻(0.084 g, 0.100 mmol) as the initiator and CHCl₃ as the solvent. Thereaction gave 28.4 g of dark viscous fluid (10,140 equivalents ofethylene per Pd). ¹ H NMR analysis (CDCl₃): 108 methyl carbons per 1000methylene carbons. ¹³ C NMRanalysis, branching per 1000 CH₂ : Totalmethyls (119.5), Methyl (36.9), Ethyl (25.9), Propyl (2.1), Butyl (11),Amyl (1.9), ≧Hexyl and end of chain (38.9). GPC (trichlorobenzene, 135°C., polystyrene reference, results calculated as linear polyethyleneusing universal calibration theory): M_(n) =10,800, M_(w) =26,800, M_(w)/M_(n) =2.47.

Example 120

Polymerization of ethylene was carried out according to example 112,using the complex (2,6-i-PrPh)₂ DABMe₂ !PdMe(OSO₂ CF₃) (0.068 g, 0.10mmol) as the initiator and CHCl₃ as the solvent. The reaction gave 5.98g of low viscosity fluid (2130 equivalents of ethylene per Pd). ¹ H NMR(CDCl₃) 0.8-1.0 (m, CH₃); 1.0-1.5 (m, CH and CH₂); 1.5-1.7 (m, CH₃CH═CH--); 1.9-2.1 (broad, --CH₂ CH═CHCH₂ --); 5.3-5.5 (m, --CH═CH--).Integration of the olefin end groups assuming one olefin per chain givesM_(n) =630 (DP=24). A linear polymer with this molecular weight andmethyl groups at both ends should have 46 methyl carbons per 1000methylene carbons. The value measured by integration is 161, thus thispolymer is highly branched.

Example 121

Polymerization of ethylene was carried out according to example 112,using the complex { (2,6-i-PrPh)₂ DABH₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻(0.082 g, 0.10 mmol) as the initiator and CHCl₃ as the solvent. Thereaction gave 4.47 g of low -viscosity fluid (1600 equivalents ofethylene per Pd). ¹ H NMR (CDCl₃) is similar to example 120. Integrationof the olefin end groups assuming one olefin per chain gives M_(n) =880(DP =31). A linear polymer with this molecular weight and methyl groupsat both ends should have 34 methyl carbons per 1000 methylene carbons.The value measured by integration is 156, thus this polymer is highlybranched.

Example 122

Polymerization of ethylene was carried out according to example 112,using the complex { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂C(O)OCH₃ }BCl(C₆F₅)₃ ⁻ (0.116 g, 0.10 mmol) as theinitiator and CHCl₃ as the solvent.The reaction gave 0.278 g of low viscosity fluid, after correcting forthe catalyst residue this is 0.160 g(57 equivalents of ethylene per Pd).M_(n) estimated by integration of olefin end groups is 300.

Example 123

The complex (2,6-i-PrPh)₂ DABMe₂ !PdMeCl (0.056 g, 0.10 mmol) was loadedinto a Schlenk flask in the drybox followed by 40 ml of dry toluene. Asolution of ethyl aluminum dichloride (1.37 ml of 0.08M solution ino-dichlorobenzene) was added while stirring. Polymerization ofethylenewas carried out using this solution according to example 112. Thereaction gave 0.255 g of low viscosity fluid, after correcting for thecatalyst residue this is 0.200 g (71 equivalents of ethylene per Pd).M_(n) estimated by integration of olefin end groups is 1300.

Example 124

Methyl acrylate was sparged with argon, dried over activated 4A sieves,passed through activity 1 alumina B in the drybox, and inhibited byaddition of 20 ppm phenothiazine. The solid complex { (2,6-i-PrPh)₂DABMe₂ !PdMe(Et₂ O)}SbF₆ ⁻ (0.084 g, 0.100 mmol) was loaded into aSchlenk flask in the drybox. The flask was connected to a Schlenk lineunder 1 atm of ethylene, and cooled to -78° C. Forty ml of CH₂ Cl₂ wasadded by syringe and after equilibrating at -78° C. under ethylene, 5 mlof methyl acrylate was added by syringe and the mixture was warmed toroom temperature under ethylene. After 40 h, the reaction was worked upby removing the solvent in vacuo togive 3.90 g of moderately viscousfluid. Integration of the ¹ H NMR spectrum showed that this copolymercontained 6.9 mole % methyl acrylate. No poly(methyl acrylate)homopolymer could be detected in this sample by ¹ H NMR. ¹ H NMR showsthat a significant fraction of the ester groups are located at the endsof hydrocarbon branches: 3.65(s, --CO₂CH₃, area=4.5), 2.3(t, --CH₂ CO₂CH₃, ester ended branches, area=3), 1.6(m, --CH₂ CH₂ CO₂ CH₃, esterended branches, area=3), 0.95-1.55(m, CH and other CH₂, area=73),0.8-0.95(m, CH₃, ends of branches or ends of chains, area=9.5) This isconfirmed by the ¹³ C NMR quantitative analysis: Mole %: ethylene(93.1), methyl acrylate (6.9), Branching per 1000 CH₂ : Totalmethyls(80.2), Methyl (30.1), Ethyl (16.8), Propyl (1.6), Butyl (6.8),Amyl (1.3), ≧Hexyl and end of chain (20.1), methyl acrylate (41.3),Ester branches CH(CH₂)_(n) CO₂ CH₃ as a % of total ester: n≧25 (47.8),n=4 (17.4), n=1,2,3 (26.8), n=0 (8).

GPC of this sample was done in THF vs. PMMA standards using a dual UV/RIdetector. The outputs of the two detectors were very similar. Since theUVdetector is only sensitive to the ester functionality, and the RIdetector is a relatively nonselective mass detector, the matching of thetwo detector outputs shows that the ester functionality of the methylacrylateis distributed throughout the entire molecular weight range ofthe polymer,consistent with a true copolymer of methyl acrylate andethylene.

A 0.503 g sample of the copolymer was fractionated by dissolving inbenzeneand precipitating partially by slow addition of MeOH. This typeof fractionation experiment is a particularly sensitive method fordetecting a low molecular weight methyl acrylate rich component since itshould be the most soluble material under the precipitation conditions.

The precipitate 0.349 g, (69%) contained 6.9 mole % methyl acrylate by ¹H NMR integration, GPC (THF, PMMA standard, RI detector): M_(n) =19,600,M_(w) =29,500, M_(w) /M_(n) =1.51. The soluble fraction 0.180 g (36%)contained 8.3 mole % methyl acrylate by ¹ H NMR integration, GPC (THF,PMMA standard, RI detector): M_(n) =11,700, M_(w) =19,800, M_(w) /M_(n)=1.70. The characterization of the two fractions shows that the acrylatecontent is only slightly higher at lowermolecular weights. These resultsare also consistent with a true copolymer of the methyl acrylate withethylene.

Example 125

Methyl acrylate was sparged with argon, dried over activated 4A sieves,passed through activity 1 alumina B in the drybox, and inhibited byaddition of 20 ppm phenothiazine. The complex (2,6-i-PrPh)₂ DABMe₂!PdMe(OSO₂ CF₃) (0.068 g, 0.10 mmol) was loaded intoa Schlenk flask inthe drybox, and 40 ml of CHCl₃ was added followed by 5 ml of methylacrylate. The septum capped flask was connected to a Schlenk line andthe flask was then briefly evacuated and refilled with ethylene from theSchlenk line. The light orange mixture was stirred underan ethyleneatmosphere at slightly above 1 atm by using a mercury bubbler. After 20h, the reaction was worked up by removing the solvent and unreactedmethyl acrylate in vacuo to give 1.75 g of a low viscosity copolymer.

¹³ C NMR quantitative analysis: Mole %: ethylene (93), methylacrylate(7), Branching per 1000 CH₂ : Total methyls (100.9), Methyl(33.8), Ethyl (19.8), Propyl (1.9), Butyl (10.1), Amyl (7.3), ≧Hexyl andend of chains (28.4), methyl acrylate (41.8). This sample is lowmolecularweight--total methyls does not include end of chain methyls.Ester branches --CH(CH2)_(n) CO₂ CH₃ as a % of total ester: n≧5 (51.3),n=4 (18.4), n=1,2,3 (24), n=0 (6.3).

Example 126

Ethylene and methyl acrylate were copolymerized according to example 125with catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }BAF⁻(0.136 g, 0.10 mmol) in CH₂ Cl₂ solvent with a reaction time of 72 hoursto give 4.93 g of copolymer.

Example 127

Ethylene and methyl acrylate were copolymerized according to example 125with catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻(0.084 g, 0.10 mmol) with a reaction time of 72 hours to give 8.19 g ofcopolymer.

Example 128

Ethylene and methyl acrylate were copolymerized according to example 125with catalyst { (2,6-i-PrPh)₂ DABH₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻(0.082 g, 0.10 mmol) to give 1.97 g of copolymer.

Example 129

Ethylene and methyl acrylate were copolymerized according to example 125with catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdMe(CH₃ CN)}SbF₆ ⁻ (0.080 g, 0.10mmol) to give 3.42 g of copolymer. The ¹ H NMR shows primarilycopolymer, but there is also a small amount of poly(methyl acrylate)homopolymer.

Example 130

Ethylene and methyl acrylate (20 ml) were copolymerized in 20 ml ofCHCl₃ according to example 125 using catalyst { (2,6-i-PrPh)₂ DABMe₂!PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻ (0.339 g, 0.40 mmol) to give 2.17 g ofcopolymer after a reaction time of 72 hours. ¹³ C NMR quantitativeanalysis: Mole %: ethylene (76.3), methyl acrylate (23.7). Branching per1000 CH₂ : Total methyls (28.7), Methyl (20.5), Ethyl (3.8), Propyl (0),Butyl (11), ≧Amyl and end of chains (13.6), methyl acrylate (138.1).Ester branches --CH(CH₂)_(n) CO₂ CH₃ as a % of total ester: n≧5 (38.8),n=4 (20), n=1,2,3 (15.7), n=0 (25.4).

Example 131

Ethylene and methyl acrylate (20 ml) were copolymerized in 20 ml ofCHCl₃ at 50° C. for 20 hours according to example 125 using catalyst {(2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻ (0.339 g, 0.40mmol) to give 0.795 g of copolymer. DSC (two heats, -150° to +150° C.,15° C./min) shows Tg=-48° C.

Example 132

A solution of the ligand (2,6-i-PrPh)₂ DAB(Me₂) (0.045 g, 0.11 mmol)dissolved in 2 ml of CHCl₃ was added to a solution of the complexPdMe(CH₃ CN)(1,5-cyclooctadiene)!+SbF₆ ⁻ (0.051 g, 0.10 mmol) in 2 ml ofCHCl₃. This mixture was combined with 35 ml of additional CHCl₃ and 5 mlof methyl acrylate in a Schlenk flask in a drybox, and then acopolymerization with ethylene was carried out according to example 125to give 1.94 g of copolymer.

Example 133

Methyl acrylate (5 ml) was added-to the solid catalyst {(2,6-i-PrPh)₂DABMe₂ !PdMe(Et₂ O)}BF₄ ⁻ (0.069 g, 0.10 mmol) followed by40 ml of CHCl₃. The addition of methyl acrylate before the CHCl₃ isoften important to avoid deactivation of the catalyst. Acopolymerization with ethylene was carried out according to example 125togive 2.87 g of copolymer.

Characterization of poly(ethylene-co-methyl acrylate) by ¹ H NMR

NMR spectra in CDCl₃ were integrated and the polymer compositions andbranching ratios were calculated. See example 124 for chemical shiftsand assignments.

    ______________________________________                     methyl acrylate                                 CH.sub.3 per                                        CO.sub.2 CH.sub.3 per    Example Yield (g)                     (mole %)    1000 CH.sub.2                                        1000 CH.sub.2    ______________________________________    124     3.9      6.9         80     42    125     1.75     7.1         104    45    126     4.93     5.6         87     34    127     8.19     6.1         87     37    128     1.97     7.3         159    50    129     3.42     9.5         86     59    130     2.17     22.8        29     137    131     0.795    41          14     262    132     1.94     6.1         80     36    133     2.87     8.2         70     49    ______________________________________

Molecular Weight Characterization

GPC was done in THF using PMMA standards and an RI detector except forexample 133 which was done in trichlorobenzene at 135° C. vs.polystyrene reference with results calculated as linear polyethyleneusinguniversal calibration theory. When polymer end groups could bedetected by ¹ H NMR (5.4 ppm, multiplet, --CH═CH--, internal doublebond), M_(n) was calculated assuming two olefinic protons per chain.

    ______________________________________    Example   M.sub.n M.sub.w   M.sub.w /M.sub.n                                      M.sub.n (.sup.1 H NMR)    ______________________________________    124       15,500  26,400    1.70    125        1,540   2,190    1.42  850    126       32,500  49,900    1.54    127       12,300  22,500    1.83    128         555     595     1.07  360    129       16,100  24,900    1.55    130         800    3,180    3.98  1,800    131                               1,100    132       15,200  26,000    1.71    133        5,010   8.740    1.75    ______________________________________

Example 134

Ethylene and t-butyl acrylate (20 ml) were copolymerized according toexample 130 to give 2.039 g of viscous fluid. ¹ H NMR of the crudeproduct showed the desired copolymer along with residual unreactedt-butylacrylate. The weight of polymer corrected for monomer was 1.84 g.The sample was reprecipitated to remove residual monomer by slowaddition of excess MeOH to a CHCl₃ solution. The reprecipitated polymerwas driedin vacuo. ¹ H NMR (CDCl₃): 2.2(t, --CH₂ CO₂ C(CH₃)₃, esterended branches), 1.6(m, --CH₂ CH₂ CO₂ C(CH₃)₃, ester ended branches),1.45(s, --C(CH₃)₃), 0.95-1.45(m, CH and other CH₂), 0.75-0.95(m, CH₃,ends of hydrocarbon branches or ends of chains). This spectrum showsthat the esters are primarily located at the ends of hydrocarbonbranches; integration gave 6.7 mole % t-butyl acrylate. ¹³ C NMRquantitative analysis, branching per 1000 CH₂ : Total methyls(74.8),Methyl (27.7), Ethyl (15.3), Propyl (1.5), Butyl (8.6), ≧Amyl andofchains (30.8), --CO₂ C(CH₃)₃ ester (43.2). Ester branches--CH(CH₂)_(n) CO₂ C(CH₃)₃ as a % of total ester: n≧5 (44.3), n=1,2,3,4(37.2), n=0 (18.5). GPC (THF, PMMA standard):M_(n) =6000 M_(w) =8310M_(w) /M_(n) =1.39.

Example 135

Glycidyl acrylate was vacuum distilled and inhibited with 50 ppmphenothiazine. Ethylene and glycidyl acrylate (5 ml) were copolymerizedaccording to Example 125 using catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻ (0.084 g, 0.10 mmol). The reaction mixture wasfiltered through a fritted glass filter to remove chloroform insolubles,and the chloroform was removed in vacuo to give 14.1 g viscous yellowoil which still contained residual unreacted glycidyl acrylate. Thesample was reprecipitated to remove residual monomer by slow addition ofexcess acetone to a CHCl₃ solution. The reprecipitated polymer was driedin vacuo to give 9.92 g of copolymer containing 1.8 mole % glycidylacrylate. ¹ H NMR (CDCl₃): 4.4, 3.9, 3.2, 2.85, ##STR84##0.95-1.5(m, CHand other CH₂), 0.75-0.95(m, CH₃, ends of hydrocarbon branches or endsof chains). This spectrum shows that the epoxide ring is intact, andthat the glycidyl ester groups are primarily located at the ends ofhydrocarbon branches. GPC (THF, PMMA standard): M_(n) =63,100 M_(w)=179,000 M_(w) /M_(n) =2.85.

¹³ C NMR quantitative analysis, branching per 1000 CH₂ : Total methyls(101.7), Methyl (32.5), Ethyl (21.3), Propyl (2.4), Butyl (9.5), Amyl(1.4), ≧Hexyl and end of chains (29.3), Ester branches --CH(CH₂)_(n) CO₂R as a % of total ester: n≧5 (39.7), n=4 (small amount), n=1,2,3 (50.7),n=0 (9.6).

A 3.24-g sample of the copolymer was dissolved in 50 mL of refluxingmethylene chloride. A solution of 0.18 g oxalic acid dihydrate in 5 mLof 1:1 chloroform-acetone was added to the solution of copolymer and thesolvent was evaporated off on a hot plate. The thick liquid was allowedtostand in an aluminum pan at room temperature overnight; the pan wasthen placed in an oven at 70° C. for 1.5 hr followed by 110° C./vacuumfor 5 hr. The cured polymer was a dark, non-tacky soft rubber which toreeasily (it had a very short elongation to break despite itsrubberiness).

Example 136

1-Pentene (20 ml) and methyl acrylate (5 ml) were copolymerized in 20 mlchloroform for 96 hours using catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂CH₂ C(O)OCH₃ }SbF₆ ⁻ (0.084 g, 0.10 mmol). The solvent and unreactedmonomers were removed in vacuo to give 0.303 g copolymer (0.219 g aftercorrecting for catalyst residue). The ¹ H NMR spectrum was similar tothe ethylene/methyl acrylate copolymer of example 124 suggesting thatmany of the ester groups are located at the ends of hydrocarbonbranches. Integration shows that the product contains 21 mole % methylacrylate. There are 65 acrylates and 96 methyls per 1000 methylenecarbons. GPC (THF, PMMA standard): M_(n) =6400 M_(w) =11200 M_(w) /M_(n)=1.76.

Example 137

Benzyl acrylate was passed through activity 1 alumina B, inhibited with50 ppm phenothiazine, and stored over activated 4A molecular sieves.Ethyleneand benzyl acrylate (5 ml) were copolymerized according toexample 135 to give 11.32 g of viscous fluid. ¹ H NMR of the crudeproduct showed a mixture of copolymer and unreacted benzyl acrylate (35wt %) The residual benzyl acrylate was removed by two reprecitations,the first by addition of excess MeOH to a chloroform solution, and thesecond by addition of excess acetone to a chloroform solution. ¹ H NMR(CDCl₃): 7.35 (broad s, --CH₂ C₆ H₅), 5.1(s, --CH₂ C₆ H₅),2.35(t, --CH₂CO₂ CH₂ C₆ H₅, ester ended branches), 1.6(m, --CH₂ CH₂ CO₂ CH₂ C₆ H₅,ester ended branches), 0.95-1.5(m, CH and other CH₂), 0.75-0.95(m, CH₃,ends of hydrocarbon branches or ends of chains). Integration shows thatthe product contains 3.7 mole % benzyl acrylate. There are 21 acrylatesand 93 methyls per 1000 methylene carbons. GPC (THF, PMMA standard):M_(n) =46,200 M_(w) =73,600 M_(w) /M_(n) =1.59.

¹³ C NMR quantitative analysis, Branching per 1000 CH₂ : Total methyls(97.2), Methyl (32.9), Ethyl (20.3), Propyl (2.4), Butyl (9.7), Amyl(2.9), ≧Hexyl and end of chains (35.2), benzyl acrylate (17.9), Esterbranches --CH(CH₂)_(n) CO₂ R as a % of total ester: n≧5 (44.5), n=4(7.2), n=1,2,3 (42.3), n=0 (6)

Example 138

1-Pentene (10 ml) and ethylene (1 atm) were copolymerized in 30 mlchloroform according to example 125 using catalyst { (2,6-i-PrPh)₂DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻ (0.084 g, 0.10 mmol) to give 9.11g highly viscous yellow oil The ¹ HNMR spectrum was similar to thepoly(ethylene) of example 110 with 113 methyl carbons per 1000 methylenecarbons. ¹³ C NMR quantitative analysis, branching per 1000 CH₂ : Totalmethyls (119.5), Methyl (54.7), Ethyl (16.9), Propyl (8.4), Butyl (7.7),Amyl (7.2), ≧Hexyland end of chains (30.9). GPC (trichlorobenzene, 135°C., polystyrene reference, results calculated as linear polyethyleneusing universal calibration theory): M_(n) =25,000, M_(w) =44,900, M_(w)/M_(n) =1.79.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc    Freq ppm  Intensity    ______________________________________    39.6012   5.53532    39.4313   6.33425       MB.sub.2    38.3004   8.71403       MB.sub.3 +    37.9446   17.7325       MB.sub.3 +    37.2809   36.416        αB.sub.1, 3B.sub.3    36.7659   5.10586       αB.sub.1, 3B.sub.3    34.3181   56.1758       αγ+B    33.8243   15.6271       αγ+B    33.3942   8.09189       MB.sub.1    32.9854   20.3523       MB.sub.1    32.6721   4.35239       MB.sub.1    32.327    4.06305       3B.sub.5    31.9394   27.137        3B.sub.6 +, 3 EOC    31.4031   9.62823       γ+γ+B, 3B.sub.4    30.235    52.8404       γ+γ+B, 3B.sub.4    29.7518   162.791       γ+γ+B, 3B.sub.4    29.3164   26.506        γ+γ+B, 3B.sub.4    27.5695   15.4471       Bγ+B, 2B.sub.2    27.1341   59.1216       Bγ+B, 2B.sub.2    26.4811   8.58222       Bγ+B, 2B.sub.2    24.4475   5.93996       ββB    23.12     5.05181       2B.sub.4    22.6369   29.7047       2B.sub.5 +, 2 EOC    20.1626   6.29481       2B.sub.3    19.7378   31.9342       1B.sub.1    19.2068   3.93019       1B.sub.1    14.2582   5.59441       1B.sub.3    13.8706   36.3938       1B.sub.4 +, 1 EOC    10.9768   9.89028       1B.sub.2    ______________________________________

Example 139

1-Pentene (20 ml) was polymerized in 20 ml chloroform according toexample 138 to give 2.59 g of viscous fluid (369 equivalents 1-penteneper Pd). Integration of the ¹ H NMR spectrum showed 118 methyl carbonsper 1000 methylene carbons. DSC (two heats, -150° to +150° C., 15°C./min) shows Tg=-58° C. and a low temperature melting endotherm from-50° C. to 30° C. (32 J/g).

¹³ C NMR quantitative analysis, branching per 1000 CH2: Total methyls(118), Methyl (85.3), Ethyl (none detected), Propyl (15.6), Butyl (nondetected), ≧Amyl and end of chains (17.1). GPC (trichlorobenzene, 135°C., polystyrene reference, results calculated as linear polyethyleneusing universal calibration theory): M_(n) =22,500, M_(w) =43,800, M_(w)/M_(n) =1.94.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    42.6277  4.69744       αα for Me & Et.sup.+    39.5428  9.5323        3.sup.rd carbon of a 6.sup.+  carbon                           side chain that has a methyl                           branch at the 4 position    38.1357  3.59535    37.8384  13.9563       MB.sub.3 +    37.5888  28.4579    37.2224  54.6811       αB.sub.1, 3B.sub.3    35.5287  6.51708    34.6366  7.35366    34.2437  22.3787    32.911   45.2064       MB.sub.1    32.5977  10.5375    32.38    4.02878    31.8809  14.1607       3B.sub.6 +, 3 EOC    30.6916  8.44427       γ.sup.+ γ.sup.+ B    30.0703  63.1613       γ.sup.+ γ.sup.+ B    29.6987  248           γ.sup.+ γ.sup.+ B    29.2633  17.9013       γ.sup.+ γ.sup.+ B    28.8916  3.60422    27.1182  66.2971       βγ.sup.+ B, (4B.sub.5, etc.)    24.5324  16.8854    22.5784  16.0395       2B.sub.5 +, 2 EOC    20.1041  13.2742    19.6952  54.39903      1B.sub.1, 2B.sub.3    14.2104  12.2831    13.8281  16.8199       1B.sub.4 +, EOC, 1B.sub.3    ______________________________________

Integration of the CH₂ peaks due to the structure --CH(R)CH₂ CH(R')--,where R is an alkyl group, and R' is an alkyl group with two or morecarbons showed that in 69% of these structures, R═Me. The regionintegrated for the structure where both R and R' are ≧Ethyl was 39.7 ppmto 41.9 ppm to avoid including an interference from another type ofmethylene carbon on a side chain.

Example 140

(2,6-i-PrPh)₂ DABMe₂ !PdMeCl (0.020 g, 0.036 mmol) was dissolvedin 4 mlCH₂ Cl₂ and methyl acrylate (0.162 g, 0.38 mmol, inhibited with 50 ppmphenothiazine) was added while stirring. This solution was added to astirred suspension of NaBAF (0.033 g, 0.038 mmol) in 4 ml of CH₂ Cl₂.After stirring for 1 hour, the mixture was filtered through a 0.5 μmPTFE membrane filter to remove a flocculent gray precipitate. Thesolvent was removed from the filtrate in vacuo to give a solid which wasrecrystallized from a CH₂ Cl₂ /pentane mixture at -40° C. to give 0.39 g(75% yield) of orange crystalline { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂C(O)OCH₃)BAF⁻. ¹ H NMR (CDCl₃): 0.65(m, CH₂, 2H);1.15-1.45(four sets ofdoublets for --CH(CH₃)₂ and multiplet at 1.4 for a CH₂, total area=26H);2.19,2.21 (s,s, CH₃ of ligand backbone, 6H); 2.40(m, CH₂, 2H); 2.90 (m,--CH(CH₃)₂, 4H); 3.05(s, --CO₂ CH₃, 3H); 7.25-7.75(m, aromatic H ofligand and counterion, 19H).

All GPC data reported for examples 141-170, 177, and 204-212 were run intrichlorobenzene vs. polyethylene standards unless otherwise indicated.All DSC data reported for examples 141-170, 177, and 204-212 (secondheat, -150° C. to 150°, 10 or 15° C./min).

Example 141

A Schlenk flask containing { (2,6-i-PrPh)₂ DABH₂ !NiMe(Et₂ O)}BAF⁻ (1.3mg, 8.3×10⁻⁷ mol) under an argon atmosphere was cooled to -78° C. Uponcooling, the argon was evacuated and theflask backfilled with ethylene(1 atm). Toluene (75 mL) was added via syringe. The polymerizationmixture was then warmed to 0° C. The solution was stirred for 30 minutes

Polymer began to precipitate from the solution within minutes. After 30minutes, the polymerization was terminated upon exposing the catalyst toair. The polymer was precipitated from acetone, collected by filtrationand washed with 6M HCl, water, and acetone. The polymer was dried invacuo. The polymerization yielded 1.53 g of polyethylene (1.3×10⁵ TO).M_(n) =91,900; M_(w) =279,000; M_(w) /M_(n) =3.03; T_(m) =129° C. ¹ HNMR (C₆ D₅ Cl, 142° C.) 0.6 methyls per 100 carbons.

Example 142

The reaction was done in the same way as in Example 141 using 1.3 mg of{ (2,6-i-PrPh)₂ DABMe₂ !NiMe(Et₂ O)}BAF⁻ (8.3×10⁻⁷ mol). The polymer wasisolated as a white solid (0.1 g).

Examples 143-148

General procedure for the polymerization of ethylene by themethylaluminoxane (MAO) activation of nickel complexes containingbidentate diimine ligands: Polymerization at 0° C.: The bisimine nickeldihalide complex (1.7×10⁻⁵ mol) was combined with toluene (100 mL) in aflame dried Schlenk flask under 1 atmosphere ethylene pressure. Thepolymerization was cooled to 0° C. in an ice-water bath. The mixture wasstirred at 0° C. for 15 minutes prior to activation with MAO.Subsequently, 1.5 mL of a 10% MAO (100 eq) solution in toluene was addedonto the nickel dihalide suspension. The solution was stirred at 0° C.for 10, 30, or 60 minutes. Within minutes increased viscosity and/orprecipitation of polyethylene was observed. The polymerization wasquenched and the polymer precipitated from acetone. The polymer wascollected by suction filtration and dried under vacuum for 24 hours. SeeTable I for a detailed description of molecular weight and catalystactivity data.

    __________________________________________________________________________    Example No.       Catalyst    __________________________________________________________________________    143                (2,6-i-PrPh).sub.2 DABH.sub.2 !NiBr.sub.2    144                (2,6-i-PrPh).sub.2 DABMe.sub.2 !NiBr.sub.2    145                (2,6-MePh).sub.2 DABH.sub.2 !NiBr.sub.2    146                (2,6-i-PrPh).sub.2 DABAn!NiBr.sub.2    147                (2,6-MePh).sub.2 DABAn!NiBr.sub.2    148                (2,6-MePh).sub.2 DABMe.sub.2 !NiBr.sub.2    __________________________________________________________________________                 TO/               Thermal              Yield                 hr · mol Analysis    Exam.        tions.sup.1              (g)                 catalyst                      M.sub.n                          M.sub.w                               M.sub.w /M.sub.n                                   (°C.)    __________________________________________________________________________    143 0° C., 30 m              5.3                 22,700                       80,900                          231,000                               2.85                                   119 (T.sub.m)    144.sup.2        0° C., 30 m              3.8                 16,300                      403,000                          795,000                               1.97                                   115 (T.sub.m)    145.sup.3        0° C., 30 m              3.4                 14,300                       42,900                          107,000                               2.49                                   131 (T.sub.m)    146.sup.2        0° C., 30 m              7.0                 29,900                      168,000                          389,000                               2.31                                   107 (T.sub.m)    147 0° C., 10 m              3.7                 47,500                      125,000                          362,000                               2.89                                   122 (T.sub.m)    148 0° C., 10 m              5.1                 65,400                      171,000                          440,000                               2.58                                   115 (T.sub.m)    __________________________________________________________________________     .sup.1 Polymerization reactions run at 1 atmosphere ethylene pressure.     .sup.2 Branching Analysis by .sup.13 C NMR per 1000 CH.sub.2 : Ex. 144:     Total methyls (54.3), Methyl (43.4), Ethyl (3.3), Propyl (2), Butyl (1.3)     ≧ Butyl and end of chains (5.7). Ex. 146: Total methyls (90.9),     Methyl (65.3), Ethyl (7.2), Propyl (4.5), Butyl (3.5), Amyl (4.5),     ≧ Hexyl and end of chains (10.2).     .sup.3 Ex. 145: .sup.1 H NMR (C.sub.6 D.sub.5 Cl), 142° C.) 0.1     methyl per 100 carbon atoms.

Examples 149-154

Polymerization at Ambient Temperature The general procedure describedfor the MAO activation of the diimine nickel dihalides was followed inthe polymerizations detailed below, except all polymerizations were runbetween 25°-30° C.

    __________________________________________________________________________    Example No.       Catalyst    __________________________________________________________________________    149                (2,6-i-PrPh).sub.2 DABH.sub.2 !NiBr.sub.2    150                (2,6-i-PrPh).sub.2 DABMe.sub.2 !NiBr.sub.2    151                (2,6-MePh).sub.2 DABH.sub.2 !NiBr.sub.2    152                (2,6-i-PrPh).sub.2 DABAn!NiBr.sub.2    153                (2,6-MePh).sub.2 DABAn!NiBr.sub.2    154                (2,6-MePh).sub.2 DABMe.sub.2 !NiBr.sub.2    __________________________________________________________________________                 TO/               Thermal              Yield                 hr · mol Analysis    Exam.        tions.sup.1              (g)                 catalyst                      M.sub.n                          M.sub.w                               M.sub.w /M.sub.n                                   (°C.)    __________________________________________________________________________    149 30° C., 30 m              2.5                 12,200                       15,500                           34,900                               2.24                                   --    150.sup.2        25° C., 30 m              3.4                 14,500                      173,000                          248,000                               1.44                                   -51 (T.sub.g)    151.sup.3        25° C., 30 m              7.2                 30,800                       13,900                           39,900                               2.88                                   90, 112                                   (T.sub.m)    152.sup.2        25° C., 30 m              4.2                 18,000                       82,300                          175,000                               2.80                                   39 (T.sub.m)    153 25° C., 10 m              4.9                 62,900                       14,000                           25,800                               1.85                                   --    154 25° C., 10 m              3.7                 47,500                       20,000                           36,000                               1.83                                   --    __________________________________________________________________________     .sup.1 Polymerization reactions run at 1 atmosphere ethylene pressure.     .sup.2 Branching Analysis by .sup.13 C NMR per 1000 CH.sub.2 : Ex. 150:     Total methyls (116.3), Methyl (93.5), Ethyl (6.2), Propyl (3.2), Butyl     (2.9), Am (6.6), ≧ Hex and end of chains (11.2). Ex. 152: Total     methyls (141.9), Methyl (98.1), Ethyl (15.9), Propyl (5.6), Butyl (6.8),     Amyl (4.1), ≧ Hex and end of chains (10.7). Quantitation of the     CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 structure per 1000 CH.sub.2 's: 8.     .sup.3 Ex. 151: .sup.1 H NMR (C.sub.6 D.sub.5 Cl), 142° C.) 3     methyl per 100 carbon atoms.

Example 155

A standard solution of (2,6-i-PrPh)₂ DABAn!NiBr₂ was prepared asfollows:1,2-difluorobenzene (10 mL) was added to 6.0 mg of (2,6-i-PrPh)₂DABAn!NiBr₂ (8.4×10⁻⁶ mol) in a 10 mL volumetric flask. The standardsolution was transferred to a Kontes flask and stored under an argonatmosphere.

The standard catalyst solution (1.0 mL, 8.4×10⁻⁷ mol catalyst) was addedto a Schlenk flask which contained 100 mL toluene, and was under1atmosphere ethylene pressure. The solution was cooled to 0° C., and 1.5mL of a 10% solution of MAO (≧1000 eq) was added. The solution wasstirred for 30 minutes. Polymer began to precipitate within minutes. Thepolymerization was quenched and the polymer precipitated fromacetone.The resulting polymer was dried in vacuo (2.15 g, 1.84 ×10⁵ TO). M_(n)=489,000; M_(w) =1,200,000; M_(w) /M_(n) =2.47

Example 156

The polymerization of ethylene at 25° C. was accomplished in anidentical manner to that described in Example 155. The polymerizationyielded 1.8 g of polyethylene (1.53×10⁵ TO). M_(n) =190,000; M_(w)=410,000; M_(w) /M_(n) =2.16; ¹ H NMR (C₆ D₅ Cl, 142° C.) 7 methyls per100 carbons.

Example 157

A standard solution of (2,6-MePh)₂ DABAn!NiBr₂ was prepared in the sameway as described for the complex in Example 155 using 5.0 mg of(2,6-MePh)₂ DABAn!NiBr₂ (8.4×10⁻⁶ mol).

Toluene (100 mL) and 1.0 mL of the standard solution of complex 5(8.3×10⁻⁷ mol catalyst) were combined in a Schlenk flask under 1atmosphere ethylene pressure. The solution was cooled to 0° C., and 1.5mL of a 10% solution of MAO(≧1000 eq) was added. The polymerizationmixture was stirred for 30 minutes. The polymerization was terminatedand the polymer precipitated from acetone. The reaction yielded1.60 g ofpolyethylene (1.4×10⁵ TO). M_(n) =590,000; M_(w) =1,350,000; M_(w)/M_(n) =2.29.

Example 158

Toluene (200 mL) and 1.0 mL of a standard solution of (2,6-i-PrPh)₂DABAn!NiBr₂ (8.3×10⁻⁷ mol catalyst) were combined in a Fisher-Porterpressure vessel. The resulting solution was cooled to 0° C., and 1.0 mLof a 10% MAO (≧1000 eq) solution in toluene was added to activate thepolymerization. Subsequent to the MAO addition, the reactor was rapidlypressurized to 276 kPa. The solution wasstirred for 30 minutes at 0° C.After 30 minutes, the reaction was quenched and polymer precipitatedfrom acetone. The resulting polymer was dried under reduced pressure.The polymerization yielded 2.13 g of white polyethylene (1.82×10⁵ TO).M_(n) =611,000; M_(w) =1,400,000; M_(w) /M_(n) =2.29; T_(m) =123° C.; ¹H NMR (C₆ D₅ Cl, 142° C.) 0.5 methyls per 100 carbons.

Examples 159-160 Polymerization of Propylene

The diimine nickel dihalide complex (1.7×10⁻⁵ mol) was combined withtoluene (100 mL) in a Schlenk flask under 1 atmosphere propylenepressure. The polymerization was cooled to 0° C., and 1.5 mL of a 10%MAO (100 eq) solution in toluene was added. The solution was stirred for2 hours. The polymerization was quenched and the polymer precipitatedfrom acetone. The polymer was dried under vacuum.

    ______________________________________    Example No.     Catalyst    ______________________________________    159              (2,6-i-PrPh).sub.2 DABH.sub.2 !NiBr.sub.2    160              (2,6-i-PrPh).sub.2 DABAn!NiBr.sub.2    ______________________________________                        TO/                     Thermal    Ex-  Condi-  Yield  hr · mol  M.sub.w /                                                Analysis    am.  tions.sup.1                 (g)    catalyst                              M.sub.n                                     M.sub.w                                           M.sub.n                                                (°C.)    ______________________________________    159  0° C.,                 1.3      900 131,000.sup.a                                     226,000                                           1.72 -20 (T.sub.g)         2 h    160  0° C.,                 4.3    2,900 147,000.sup.                                     235,000                                           1.60 -78, -20         2 h                                    (T.sub.g)    ______________________________________     .sup.a GPC (toluene, polystyrene standard)

Ex. 159: ¹ H NMR (C₆ D₅ Cl), 142° C.) 30 methyls per 100 carbon atoms.

Ex. 160: ¹ H NMR (C₆ D₅ Cl), 142° C.) 29 methyls per 100 carbon atoms.Quantitative ¹³ C NMR analysis, branching per 1000 CH₂ : Total methyls(699). Based on the total methyls, the fraction of 1,3-enchainment is13%. Analysis of backbone carbons (per 1000 CH₂): δ⁺ (53), δ⁺ /γ (0.98).

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 140C, 0.05M CrAcAc    Freq ppm  Intensity    ______________________________________    47.3161   53.1767    46.9816   89.3849    46.4188   82.4488    45.84     23.1784    38.4702   12.8395    38.0985   29.2643    37.472    18.6544    37.2915   24.8559    35.3747   15.6971    34.5623   14.6353    33.3145   14.2876    32.996    12.2454    30.9464   24.2132    30.6703   57.4826    30.081    30.122          γ to single branch    29.6987   29.2186         δ.sup.+  to branch    28.3659   298.691    27.4792   33.2539    27.1235   29.7384    24.5324   9.45408    21.1554   20.0541    20.6244   110.077    19.9926   135.356    16.9342   8.67216    16.4829   8.81404    14.9962   8.38097    ______________________________________

Example 161

(2,6-i-PrPh)₂ DABH₂ !NiBr₂ (10 mg, 1.7×10⁻⁵ mol)was combined withtoluene (40 mL) under a N₂ atmosphere. A 10% solution of MAO (1.5 mL,100 eq) was added to the solution. After 30 minutes, the Schlenk flaskwas backfilled with propylene. The reaction wasstirred at roomtemperature for 5.5 hours. The polymerization was quenched,and theresulting polymer dried under vacuum (670 mg, 213 TO/h). M_(n) =176,000;M_(w) =299,000; M_(w) /M_(n) =1.70. Quantitative ¹³ CNMR analysis,branching per 1000 CH₂ : Total methyls (626), Methyl (501), Ethyl (1),≧Butyl and end of chain (7). Based on the total methyls, the fraction of1,3-enchainment is 22%. Analysis of backbone carbons (per 1000 CH₂): δ⁺(31), δ⁺ /γ (0.76).

Examples 162-165

The diimine nickel dihalide catalyst precursor (1.7×10⁻⁵ mol) wascombined with toluene (40 mL) and 1-hexene (10 mL) under a N₂atmosphere. Polymerization reactions of 1-hexene were run at both 0° C.and room temperature. A 10% solution of MAO (1.5 mL, 100 eq) in toluenewas added. Typically the polymerization reactions were stirred for 1-2hours. The polymer was precipitated from acetone and collected bysuction filtration. The resulting polymer was dried under vacuum.

    __________________________________________________________________________    Ex. No.           Catalyst    __________________________________________________________________________    162                (2,6-i-PrPh).sub.2 DABH.sub.2 !NiBr.sub.2    163                (2,6-i-PrPh).sub.2 DABAn!NiBr.sub.2    164                (2,6-i-PrPh).sub.2 DABH.sub.2 !NiBr.sub.2    165                (2,6-i-PrPh).sub.2 DABAn!NiBr.sub.2    __________________________________________________________________________                 TO/               Thermal              Yield                 hr · mol Analysis    Exam.        tions.sup.1              (g)                 catalyst                      M.sub.n                          M.sub.w                               M.sub.w /M.sub.n                                   (°C.)    __________________________________________________________________________    162 25° C., 1 h              3.0                 2100 173,000                          318,000                               1.84                                   -48 (T.sub.g)    163 25° C., 1 h              1.2                  860 314,000                          642,000                               2.05                                   -54 (T.sub.g)                                   -19 (T.sub.m)    164  0° C., 2 h              3.0                 1100  70,800                          128,000                               1.80                                   -45 (T.sub.g)    165  0° C., 2 h              1.5                  540  91,700                          142,000                               1.55                                   -49 (T.sub.g)    __________________________________________________________________________     .sup.a GPC (toluene, polystyrene standards).

Branching Analysis Ex. 162: by ¹³ C NMR per 1000 CH₂ :

Total methyls (157.2), Methyl (47), Ethyl (1.9), Propyl (4.5), Butyl(101.7), ≧Am and end of chain (4.3).

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    42.8364  7.99519        Methine    41.3129  27.5914        αα to two Eth.sup.+  branches    40.5759  19.6201        αα to two Eth.sup.+  branches    37.8831  14.7864        Methines and Methylenes    37.2984  93.6984        Methines and Methylenes    36.6684  6.99225        Methines and Methylenes    35.5773  36.067         Methines and Methylenes    34.655   55.825         Methines and Methylenes    34.3091  63.3862        Methines and Methylenes    33.8356  24.1992        Methines and Methylenes    33.428   53.7439        Methines and Methylenes    32.9957  51.1648        Methines and Methylenes    31.9169  17.4373        Methines and Methylenes    31.5546  14.008         Methines and Methylenes    31.1552  10.6667        Methines and Methylenes    30.5993  34.6931        Methines and Methylenes    30.274   56.8489        Methines and Methylenes    30.1258  42.1332        Methines and Methylenes    29.747   97.9715        Methines and Methylenes    29.1047  47.1924        Methines and Methylenes    28.8823  64.5807        Methines and Methylenes    28.1289  13.6645        Methines and Methylenes    27.5648  61.3977        Methines and Methylenes    27.1777  50.9087        Methines and Methylenes    27.0213  31.6159        Methines and Methylenes    26.9142  31.9306        Methines and Methylenes    26.4572  4.715666       Methines and Methylenes    23.2085  154.844        2B.sub.4    22.6074  12.0719        2B.sub.5 +, EOC    20.0669  8.41495        1B.sub.1    19.6963  57.6935        1B.sub.1    15.9494  17.7108    14.3477  8.98123    13.8742  248            1B.sub.4 +, EOC    ______________________________________

Example 166

(2,6-i-PrPh)₂ DABMe₂ !NiBr₂ (10.4 mg, 1.7×10⁻⁵ mol) was combined withtoluene (15 mL) and 1-hexene (40 mL) under 1 atmosphere ethylenepressure. The solution was cooled to 0° C., and1.5 mL of a 10% MAO (100eq) solution in toluene was added. The reaction was stirred at 0° C. for2.5 hours. The polymerization was quenchedand the polymer precipitatedfrom acetone. The resulting polymer was dried under reduced pressure(1.4 g). Mn=299,000; Mw=632,000; Mw/Mn=2.12.

Branching Analysis by ¹³ C NMR per 1000 CH₂ : Total methyls (101.3),Methyl (36.3), Ethyl (1.3), Propyl (6.8), Butyl (47.7), ≧Amyl and end ofchains (11.5).

Example 167

(2,6-i-PrPh)₂ DABH₂ !NiBr₂ (10 mg, 1.7×10⁻⁵ mol)was added to a solutionwhich contained toluene (30 mL) and 1-octene (20 mL) under 1 atmethylene. A 10% solution of MAO (1.5 mL, 100 eq) in toluene was added.The resulting purple solution was allowed to stir for 4hours at roomtemperature. Solution viscosity increased over the duration of thepolymerization. The polymer was precipitated from acetone and driedundervacuum resulting in 5.3 g of copolymer. M_(n) =15,200, M_(w) =29,100,M_(n) /M_(w) =1.92.

Example 168

(2,6-i-PrPh)₂ DABAn!NiBr₂ (12 mg, 1.7×10⁻⁵ mol) was combined withtoluene (75 mL) in a Schlenk flask under 1 atmosphere ethylene pressure.The mixture was cooled to 0° C., and 0.09 mL of a 1.8M solution intoluene of Et₂ AlCl (10 eq) was added. The resulting purple solution wasstirred for 30 minutes at 0° C. The polymerization was quenched and thepolymer precipitated from acetone. Theresulting polymer was dried underreduced pressure (6.6 g, 2.8×10⁴ TO). M_(n) =105,000; M_(w) =232,000;M_(w) /M_(n) =2.21

Example 169

(2,6-i-PrPh)₂ DABAn!NiBr₂ (12 mg, 1.7×10⁻⁵ mol) was combined withtoluene (75 mL) under 1 atmosphere propylene pressure. The solution wascooled to 0° C. and 0.1 mL of Et₂ AlCl (≧10 eq) was added. The reactionwas stirred at 0° C. for 2 hours. The polymerization was quenched andthe polymer precipitated from acetone. The resulting polymer was driedunder reduced pressure (3.97 g, 2800 TO).

Example 170

(2,6-i-PrPh)₂ DABAn!NiBr₂ (12 mg, 1.7×10⁻⁵ mol) was combined withtoluene (50 mL) and 1-hexene (25 mL) under a N₂ atmosphere. Et₂ AlCl(0.01 mL, 10 eq) was added to the polymerizationmixture. The resultingpurple solution was allowed to stir for 4 hours. After 4 hours thepolymerization was quenched and the polymer precipitatedfrom acetone.The polymerization yielded 1.95 g poly(1-hexene) (348 TO/h). M_(n)=373,000; M_(w) =680,000; M_(w) /M_(n) =1.81.

Example 171

1-Tetradecene (20 ml) was polymerized in methylene chloride (10 ml) for20 hr using catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃}SbF₆ ⁻ (0.04 g, 0.05 mmol). The solvent and reacted monomer wereremoved in vacuo. The polymer was precipitated toremove unreactedmonomer, by the addition of acetone to a chloroform solution. Theprecipitated polymer was dried in vacuo to give a 10.2 g yield. ¹³ C NMR(trichlorobenzene, 120° C.) integrated to givethe following branchinganalysis per 1000 methylene carbons: Total methyls (69.9), methyl(24.5), ethyl (11.4), propyl (3.7), butyl (2.3) amyl (0.3), ≧Hexyl andend of chain (24.2). Thermal analysis showed Tg=-42.7° C., and Tm=33.7°C. (15.2 J/g).

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc    Freq ppm   Intensity    ______________________________________    39.3416    7.78511         MB.sub.2    38.2329    5.03571         MB.sub.3 +    37.8616    9.01667         MB.sub.3 +    37.5857    3.33517         MB.sub.3 +    37.2462    31.8174         αB.sub.1, 3B.sub.3    36.6415    2.92585         αB.sub.1, 3B.sub.3    34.668     5.10337         αγ.sup.+ B    34.2384    38.7927         αγ.sup.+ B    33.7397    16.9614         3B.sub.5    33.3471    3.23743         3B.sub.6 +, 3 EOC    32.9387    16.0951         γ.sup.+ γ.sup.+ B, 3B.sub.4    31.9148    27.6457         γ.sup.+ γ.sup.+ B, 3B.sub.4    31.1297    6.03301         γ.sup.+ γ.sup.+ B, 3B.sub.4    30.212     59.4286         γ.sup.+ γ.sup.+ B, 3B.sub.4    29.7398    317.201         γ.sup.+ γ.sup.+ B, 3B.sub.4    29.3101    32.1392         γ.sup.+ γ.sup.+ B, 3B.sub.4    27.1511    46.0554         βγ.sup.+ B, 2B.sub.2    27.0185    53.103          βγ.sup.+ B, 2B.sub.2    26.419     9.8189          βγ.sup.+ B, 2B.sub.2    24.244     2.46963         ββB    22.6207    28.924          2B.sub.5 +, 2 EOC    20.0479    3.22712         2B.sub.3    19.7084    18.5679         1B.sub.1    14.3929    3.44368         1B.sub.3    13.8677    30.6056         1B.sub.4 +, 1 EOC    10.9448    9.43801         1B.sub.2    ______________________________________

Example 172

4-Methyl-1-pentene (20 ml) was polymerized in methylene chloride (10 ml)for 19 hr using catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃}SbF₆ ⁻ (0.04 g, 0.05 mmol). The solvent and unreacted monomer wereremoved in vacuo. The polymer was precipitated to remove residualmonomer by addition of excess acetone to achloroform solution. Theprecipitated polymer was dried in vacuo to give a 5.7 g yield. ¹³ C NMR(trichlorobenzene, 120° C.) integrated to give 518 methyls per 1000methylene carbon atoms. Thermal analysis showed Tg -30.3° C.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc           Freq ppm                  Intensity    ______________________________________           47.8896                  13.3323           47.4011                  8.54293           45.7127                  26.142           45.1392                  17.4909           43.9658                  13.9892           43.1375                  12.7089           42.6171                  11.5396           41.8207                  9.00437           39.203 64.9357           37.9712                  24.4318           37.3075                  87.438           35.4862                  16.3581           34.9553                  24.5286           34.35  31.8827           33.3624                  25.7696           33.0226                  42.2982           31.4403                  25.3221           30.6226                  38.7083           28.504 26.8149           27.989 81.8147           27.7341                  78.3801           27.5802                  94.6195           27.458 75.8356           27.0864                  35.5524           25.6103                  97.0113           23.4333                  59.6829           23.0563                  41.5712           22.536 154.144           21.9944                  5.33517           20.7307                  16.294           20.4971                  34.7892           20.2953                  29.9359           19.7378                  62.0082    ______________________________________

Example 173

1-Eicosene (19.0 g) was polymerized in methylene chloride (15 ml) for 24hrusing catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻(0.047 g, 0.05 mmol). The solvent and unreacted monomer were removed invacuo. The polymer was precipitated to remove residual monomer byaddition of excess acetone to a chloroform solution of the polymer. Thesolution was filtered to collect the polymer.The precipitated polymerwas dried in vacuo to give a 5.0 g yield. ¹³ C NMR quantitativeanalysis, branching per 1000 CH2: Total methyls (27), Methyl (14.3),Ethyl (0), Propyl (0.2), Butyl (0.6), Amyl (0.4), ≧Hexyl and end ofchains (12.4).

Integration of the CH₂ peaks due to the structure --CH(R)CH₂ CH(R')--,where R is an alkyl group, and R' is an alkyl group with two or morecarbons showed that in 82% of these structures, R═Me.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc    Freq ppm  Intensity    ______________________________________    37.7853   33.978          MB.sub.2.sup.+    37.1428   52.1332         αB    34.1588   41.067          αB.sub.4 +    32.826    26.6707         MB.sub.1    31.8066   24.9262         3B.sub.6.sup.+, 3 EOC    30.0703   96.4154         γ.sup.+ γ.sup.+ B, 3B.sub.4    29.6243   1239.8          γ.sup.+ γ.sup.+ B, 3B.sub.4    27.0013   78.7094         Bγ.sup.+ B, (4B.sub.5, etc.)    22.5041   23.2209         2B.sub.5.sup.+, 2 EOC    19.605    30.1221         1B.sub.1    13.759    23.5115         1B.sub.4.sup.+, EOC    ______________________________________

Example 174

The complex (2,6-i-PrPh)₂ DABH₂ !PdMeCl (0.010 g, 0.019 mmol) andnorbornene (0.882 g, 9.37 mmol) were weighed into a vial and dissolvedin2 ml CH₂ Cl₂. NaBAF (0.032 g, 0.036 mmol) was rinsed into the stirringmixture with 2 ml of CH₂ Cl₂ After stirring about 5 minutes, there wassudden formation of a solid precipitate. Four ml of o-dichlorobenzenewas added and the solution became homogenous and slightly viscous. Afterstirring for 3 days, the homogeneous orange solution was moderatelyviscous. The polymer was precipitated by addition of the solution toexcess MeOH, isolated by filtration, and dried in vacuoto give 0.285 g(160 equivalents norbornene per Pd) bright orange glassy solid. DSC (twoheats, 15° C./min) showed no thermal events from -50° to 300° C. This isconsistent with addition type poly(norbornene). Ring-openingpolymerization of norbornene is known to produce an amorphous polymerwith a glass transition temperature of about 30°-55° C.

Example 175

The solid complex { (2,6-i-PrPh)₂ DABH₂ !PdMe(Et₂ O)}SbF₆ ⁻ (0.080 g,0.10 mmol) was added as a solid to a stirringsolution of norbornene(1.865 g) in 20 ml of o-dichlorobenzene in the drybox. About 30 minafter the start of the reaction, there was slight viscosity (foam onshaking) and the homogeneous mixture was dark orange/red. After stirringfor 20 h, the solvent and unreacted norbornene were removed in vacuo togive 0.508 g orange-red glassy solid (54 equivalents norbornene/Pd). ¹ HNMR (CDCl₃): broad featureless peaks from 0.8-2.4 ppm, no peaks in theolefinic region. This spectrum is consistent with addition typepoly(norbornene). GPC (trichlorobenzene, 135° C., polystyrene reference,results calculated as linear polyethylene using universal calibrationtheory): Mn=566 Mw=1640 Mw/Mn=2.90.

Example 176

4-Methyl-1-pentene (10 ml) and ethylene (1 atm) were copolymerized in 30mlof chloroform according to example 125 using catalyst { (2,6-i-PrPh)₂DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻ (0.084 g, 0.10 mmol) to give23.29 g highly viscous yellow oil. The ¹H NMR spectrum was similar tothe poly(ethylene) of example 110 with 117 methyl carbons per 1000methylene carbons. ¹³ C NMR quantitative analysis, branching per 1000CH² : Total methyls (117.1), Methyl (41.5), Ethyl (22.7), Propyl (3.3),Butyl (13), Amyl (1.2), ≧Hexyl and end of chains (33.1), ≧Amyl and endof chains (42.3), By ¹³ C NMR this sample contains two identifiablebranches at low levelsattributable to 4-methyl-1-pentene. The Bu and≧Amyl peaks contain small contributions from isopropyl ended branchstructures.

Example 177

CoCl₂ (500 mg, 3.85 mmol) and (2,6-i-PrPh)₂ DABAn (2.0 g, 4.0 mmol) werecombined as solids and dissolved in 50 mL of THF. The brown solution wasstirred for 4 hours at 25° C. The solvent was removed under reducedpressure resulting in a brown solid (1.97 g, 82% yield).

A portion of the brown solid (12 mg) was immediately transferred toanotherSchlenk flask and dissolved in 50 mL of toluene under 1atmosphere of ethylene. The solution was cooled to 0° C., and 1.5 mL ofa 10% MAOsolution in toluene was added. The resulting purple solutionwas warmed to 25° C. and stirred for 12 hours. The polymerization wasquenched and the polymer precipitated from acetone. The white polymer(200 mg) was collected by filtration and dried under reduced pressure.M_(n) =225,000, M_(w) =519,000, M_(w) /M_(n) =2.31, T_(g) =-42°, T_(m)=52° C. and 99.7° C.

Example 178

Ethyl 10-undecenoate (10 ml) and ethylene (1 atm) were copolymerized in30 ml of CH₂ Cl₂ according to example 125 using catalyst ( (2,6-i-PrPh)₂DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻ (0.084 g, 0.10 mmol). Thecopolymer was precipitated by removing most of the CH₂ Cl₂ in vacuo,followed by addition of excess acetone. The solution was decanted andthe copolymerwas dried in vacuo to give 1.35 g viscous fluid. ¹ H NMR(CDCl₃):0.75-0.95(m, CH₃); 0.95-1.5(m, --C(O)OCH2CH₃, CH₂, CH);1.5-1.7(m, --CH₂ CH₂ C(O)OCH₂ CH₃); 1.9-2.0(m, --CH₂ CH═CH--); 2.3(t,--CH₂ CH₂ C(O)OCH₂ CH₃); 4.15(q, --CH₂ CH₂ C(O)OCH₂ CH₃); 5.40(m,--CH═CH--). The olefinic and allylic peaks are due to isomerizedethyl10-undecenoate which has coprecipitated with the copolymer.Adjusting for this, the actual weight of copolymer in this sample is1.18 g. The copolymer was reprecipitated by addition of excess acetoneto a chloroformsolution. ¹ H NMR of the reprecipitated polymer issimilar except there are no peaks due to isomerized ethyl 10-undecenoateat 1.9-2.0 and 5.40 ppm. Based on integration, the reprecipitatedcopolymer contains 7.4 mole % ethyl 10-undecenoate, and 83 methylcarbons per 1000 methylene carbons. ¹³ C NMR quantitative analysis,branching per 1000 CH² : Total methyls (84.5), Methyl (31.7),Ethyl(16.9), Propyl (1.5), Butyl (7.8), Amyl (4.4), ≧Hexyl and end ofchains (22.3). GPC (THF, PMMA standard): Mn=20,300 Mw=26,300 Mw/Mn=1.30.¹³ C NMR quantitative analysis, branching per 1000 CH2: ethyl ester(37.8), Ester branches --CH(CH₂)nCO₂ CH₂ CH₃ as a % of total ester: n≧5(65.8), n=4 (6.5), n=1,2,3 (26.5), n=0 (1.2).

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data           Freq ppm                  Intensity    ______________________________________           59.5337                  53.217           39.7234                  2.57361           39.3145                  7.80953           38.2207                  11.9395           37.8437                  20.3066           37.2225                  29.7808           36.7181                  5.22075           34.6792                  17.6322           34.265 107.55           33.7181                  21.9369           33.3093                  8.22574           32.9164                  15.0995           32.396 8.52655           32.0828                  5.79098           31.9075                  37.468           31.127 13.8003           30.6757                  8.38026           30.2084                  52.5908           29.9961                  27.3761           29.72  151.164           29.5076                  39.2815           29.2899                  69.7714           28.727 6.50082           27.5164                  20.4174           26.9908                  64.4298           26.5713                  9.18236           26.3749                  11.8136           25.5519                  4.52152           25.0528                  43.7554           24.2457                  7.9589           23.1094                  10.0537           22.9926                  4.71618           22.6156                  37.2966           20.0245                  2.4263           19.6847                  25.9312           19.1643                  5.33693           17.5183                  2.20778           14.2954                  66.1759           13.8653                  43.8215           13.414 2.52882           11.1521                  5.9183           10.9237                  14.9294           174.945                  3.27848           172.184                  125.486           171.695                  4.57235    ______________________________________

Example 179

The solid complex { (2,6-i-PrPh)₂ DABH₂ !PdMe(Et₂ O)}SbF₆ ⁻ (0.080 g,0.10 mmol) was added as a solid to a stirringsolution of cyclopentene(1.35 g, 20 mmol) in 20 ml of dichlorobenzene in the drybox. Afterstirring 20 h, the slightly viscous solution was worked up by removingthe solvent in vacuo to give 1.05 g sticky solid (156 equivalents ofcyclopentene per Pd). ¹ H NMR (CDCl₃): complex spectrum from 0.6-2.6 ppmwith maxima at 0.75, 1.05, 1.20, 1.55, 1.65, 1.85, 2.10, 2.25, and 2.50.There is also a multiplet for internal olefin at 5.25-5.35. This isconsistent with a trisubstituted cyclopentenyl end group with a singleproton (W. M. Kelly et. al., Macromolecules 1994, 27, 4477-4485.)Integration assuming one olefinic proton per polymer chain gives DP=8.0and Mn=540. IR (Thin film between NaCl plates, cm⁻¹): 3048 (vw, olefinicend group, CH stretch), 1646(vw, olefinic end group, R₂ C=CHRtrisubstituted double bond stretch), 1464(vs), 1447(vs), 1364(m),1332(m), 1257(w), 1035(w), 946(m), 895(w), 882(w), 803(m, cyclopentenylend group, R₂ C═CHR trisubstituted double bond, CH bend), 721(vw,cyclopentenyl end group, RHC═CHR disubstituted double bond, CH bend).GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as linear polyethylene using universal calibration theory):M_(n) =138 M_(w) =246 M_(w) /M_(n) =1.79.

Example 180

The solid complex { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻(0.084 g, 0.10 mmol) was added to a stirring solution of 10.0 mlcyclopentene in 10 ml CHCl₃ in the drybox. After stirring for 20 h, themixture appeared to be separated intotwo phases. The solvent andunreacted monomer were removed in vacuo leaving2.20 g off-white solid(323 equivalents cyclopentene per Pd). DSC (25 to 300° C., 15° C./min,first heat): Tg=107° C., Tm (onset)=165° C., Tm (end)=260° C., Heat offusion=29 J/g.

Similar results were obtained on the second heat. GPC (trichlorobenzene,135° C., polystyrene reference, results calculated as linearpolyethylene using universal calibration theory): M_(n) =28,700 M_(w)=33,300 M_(w) /M_(n) =1.16.

Listed below are the ¹³ C NMR analysis for this polymer.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc           Freq ppm                  Intensity    ______________________________________           46.4873                  142.424           38.339 59.7617           30.5886                  137.551    ______________________________________

Example 181

The solid complex { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }SbF₆ ⁻(0.084 g, 0.10 mmol) was added to a stirring solution of 10.0 mlcyclopentene in 10 ml CHCl₃ in a Schlenk flask. The flask was evacuatedbriefly and refilled with ethylene.It was maintained under slightlyabove 1 atm ethylene pressure using a mercury bubbler. After 20 h, thesolvent and unreacted monomers were removed in vacuo from thehomogeneous solution to give 12.89 g of highly viscous fluid. ¹ H- NMR(CDCl₃): cyclopentene peaks: 0.65(m, 1H); 1.15(broad s, 2H); 1.5-2.0(m,5H); ethylene peaks: 0.75-0.95(m, CH₃); 0.95-1.5(m, CH and CH₂).Integration shows 24 mole % cyclopentene in this copolymer. Analysis ofthe polyethylene part of the spectrum (omitting peaks due to cyclopentylunits) shows 75 total methyl carbons per 1000 methylene carbons. Basedon quantitative ¹³ C analysis, the distribution of branches per 1000methylene carbons is Methyl (21), Ethyl (13), Propyl (˜0), Butyl (20)and ≧Amyl (20). DSC (first heat: 25° to 150° C., 10° C./min; first cool:150° to -150° C., 10° C./min; second heat: -150° to 150° C., 10°C./min,; values of secondheat reported): Tg=-33° C., Tm=19° C. (11 J/g).GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as linear polyethylene using universal calibration theory):M_(n) =3,960 M_(w) =10,800 M_(w) /M_(n) =2.73.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc    Freq ppm  Intensity    ______________________________________    48.344    1.85262    46.5562   22.8938       1 cme and/or 1,3 ccmcc    44.9064   10.8003       1,3 cme    42.0842   16.824    40.7845   117.364       2 eme    40.5777   113.702       1,3 eme    40.3336   136.742       1,3 eme    39.5591   15.0962       methylene from 2 cmc                            or/and 2 cme    38.7634   18.636    38.4716   12.3847    38.2488   17.3939    37.2144   17.5837    36.721    111.057    36.2913   11.0136    35.8776   22.0367    35.6176   90.3685    34.5248   15.734    34.1959   24.7661    33.0182   14.0261    31.8671   238.301    31.4056   20.6401    30.8433   11.2412    30.4613   20.2901    30.0104   62.2997    29.7133   78.3272    29.2359   31.6111    28.9653   53.5526    28.6577   64.0528    26.9813   17.6335    26.3925   4.51208    25.9363   5.6969    24.2971   1.70709    22.9019   9.13305       2B.sub.4    22.6048   14.3641       2B.sub.5 +, 2 EOC    19.7349   10.124        1B.sub.1    19.1991   2.00384       1B.sub.1    17.5811   2.28331       end group    13.8783   26.3448       1B.sub.4 +, 1 EOC    12.6264   19.6468       end group    10.9501   4.96188       1B.sub.2    ______________________________________

Example 182

1-Pentene (10 ml) and cyclopentene (10 ml) were copolymerized in 20 mlof o-dichlorobenzene solvent according to example 180. After 72 h, theunreacted monomers and part of the solvent were removed in vacuo to give3.75 g highly viscous fluid. Analysis by ¹ H NMR showed that thismaterial contained 1.81 g of copolymer; the remainder waso-dichlorobenzene. The ¹ H NMR spectrum was very similar topoly(ethylene-co-cyclopentene) in Example 181. Integration shows 35 mole%cyclopentene in this copolymer. Analysis of the poly(1-pentene) part ofthespectrum (omitting peaks due to cyclopentyl units) shows 62 methylcarbons per 1000 methylene carbons. The fraction of ω,1-enchainment(chain straightening) in this section is 72%. Based on quantitative ¹³ Canalysis, the distribution of branches per 1000 methylene carbons isMethyl (36), Propyl (7), and ≧Amyl (20). DSC (first heat: -150° to 150°C., 15° C./min; first cool: 150°to -150° C., 15° C./min; second heat:-150° to 150° C., 15° C./min,; values of second heat reported): Tg=-19°C., Tm=50° C. (24 J/g). GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as linear polyethylene using universalcalibration theory): Mn=14,900 Mw=27,300 Mw/Mn=1.82.

Example 183

A 100 mL autoclave was charged with chloroform (40 mL), methyl acrylate(10mL), { (2,6-EtPh)₂ DABMe₂ !PdMe(NCMe)}BAF⁻ (0.100 g 0.073 mmol), andethylene (2.1 MPa). The reaction mixture was stirred under 1.4 MPa ofethylene for 180 min; during this time the temperature inside thereactor remained between 25 and 26° C. The ethylene pressure was thenvented, and the crude reaction mixture discharged from the reactor. Thereactor was washed with 2×50 mL of chloroform. The washings wereadded tothe crude reaction mixture; 250 mL of methanol was added to theresulting solution. After standing overnight, the polymer product hadprecipitated from solution; it was isolated by decanting off thechloroform/methanol solution, and dried giving 3.91 g of an extremelyviscous oil. ¹ H NMR of this material showed it to beethylene/methylacrylate copolymer, containing 1.1 mole % methylacrylate. The polymer contained 128 methyl-ended hydrocarbon branchesper 1000 methylenes, and 7methyl ester ended branches per 1000methylenes.

Example 184

A solution of { (Np)₂ DABMe₂ !PdMe(NCMe)}SbF₆ ⁻ (0.027 g, 0.02 mmol) in5 mL CDCl₃ was agitated under 1.4 MPa of ethylene for 3 h; during thistime the temperature inside the reactor varied between 25° and 40° C. ¹H NMR of the solution indicated the presence of ethylene oligomers. Mnwas calculated on the basis of ¹ H NMR integration of aliphatic vs.olefinic resonances to be 100. The degree of polymerization, DP, wascalculated on the basis of the ¹ H NMR spectrum to be 3.8; for a linearpolymer this would result in 500 methyl-ended branches per 1000methylenes. However, based onthe ¹ H NMR spectrum the number ofmethyl-ended branches per 1000 methylenes was calculated to be 787.

Example 185 (2-t-BuPh)₂ DABMe₂ !NiBr₂

A Schlenk tube was charged with 0.288 g (0.826 mmol) of (2-t-BuPh)₂DABMe₂, which was then dissolved in 15 mL of CH₂ Cl₂. This solution wascannulated onto a suspension of (DME)NiBr₂ (0.251 g, 0.813 mmol) in 15mL of CH₂ Cl₂. The reaction mixture was allowed to stir overnight,resulting in a deep red solution. The solution was filtered and thesolvent evaporated under vacuum. The remaining orange, oily residue waswashed with ether (2×10 mL) and dried undervacuum to give an orange/rustpowder (0.36 g, 78%).

Example 186 (2-t-BuPh)₂ DABAn!NiBr₂

(2-t-BuPh)₂ DABAn (0.202 g, 0.454 mmol) and (DME)NiBr₂ (0.135 g, 0.437mmol) were combined and stirred in 25 mL of CH₂ Cl₂, as inExample 185.An orange/rust solid was isolated (0.18 g, 62%).

Example 187 (2,5-t-BuPh)₂ DABAn!NiBr₂

The corresponding diimine (0.559 g, 1.00 mmol) and (DME)NiBr₂ (0.310 g,1.00 mmol) were combined and stirred in 35 mL of CH₂ Cl₂, as was done inExample 185. An orange solid was isolated (0.64 g, 83%).

Examples 188-190

Polymerizations were carried out at 0° C. and under 1 atmosphere ofethylene pressure. The (diimine)NiBr₂ complex (1.4-1.7×10⁻⁵ mol) wasplaced into a flame-dried Schlenk flask and dissolved in 100 mL oftoluene. The flask was placed under ethylene and cooled in an ice bath.Polymerization was initiated by addition of 100equivalents (1.5 mL 10%soln in toluene) of methylaluminoxane (MAO). The reaction mixture wasstirred for 30 or 120 minutes at constant temperaturefollowed byquenching with 6M HCl. Polymer was precipitated from the resultingviscous solution with acetone, collected via filtration, and dried undervacuum for 24 h. A summary of results is shown below.

    ______________________________________    Ex No.         Catalyst    ______________________________________    188             (2-t-BuPh).sub.2 DABMe.sub.2 !NiBr.sub.2    189             (2-t-BuPh).sub.2 DABAn!NiBr.sub.2    190             (2,5-t-BuPh).sub.2 DABAn!NiBr.sub.2    ______________________________________            Catalyst              Yield                                       TO/hr · mol    Exam.   (10.sup.-5 mol)                       Conditions (g)  catalyst    ______________________________________    188     (1.7)      0° C., 120 m                                  9.88 10,500    189     (1.4)      0° C., 30 m                                  8.13 40,500    190     (1.5)      0° C., 30 m                                  6.60 31,000    ______________________________________

Examples 191-196

General Procedure. The procedure of Example 84 for thehomopolymerization of ethylene) was followed with the exception that theacrylate was added to the reaction mixture at -78° C. immediatelyfollowing the addition of 50 mL of CH₂ Cl₂. Polymerizations are at roomtemperature (rt) and 1 atm ethylene unless stated otherwise. Thecopolymers were generally purified by filtering an Et₂ O orpetroleumether solution of the polymer through Celite and/or neutralalumina. ¹H and ¹³ C NMR spectroscopic data and GPC analysis areconsistent withthe formation of random copolymers. In addition to thepolyethylene resonances, the following resonances diagnostic of acrylateincorporation were observed:

Methyl Acrylate: ¹ H NMR (CDCl₃, 400 MHz) δ3.64 (s, OMe), 2.28 (t,J=7.48, OCH₂), 1.58 (m, OCH₂ CH₂); ¹³ C NMR (C₆ D₆, 100 MHz) δ176(C(O)), 50.9 (C(O)OMe).

Fluorinated Octyl Acrylate (FOA, 3M Co.

Minneapolis, Minn.): ¹ H NMR (CDCl₃, 400 MHz) δ4.58 (t, J =13.51, OCH₂(CF₂)₆ CF₃), 2.40 (t, J=7.32, C(O)CH₂), 1.64 (m, C(O)CH₂ CH₂); ¹³ C NMR(CDCl₃,100 MHz) δ172.1 (C(O)), 59.3 (t, J_(CF) =27.0, OCH₂ (CF₂)₆ CF₃).

    __________________________________________________________________________       Catalyst       (R1,       conc.            Acrylate,                 Rxn   % Acry-                             # CH3/       (10.sup.-3            conc.                 Time                    Yield                       late Inc.                             1000    Ex.       Molar)            (Molar)                 (h)                    (g)                       mol %/wt %                             CH.sub.2                                 M.sub.w                                     M.sub.n                                         PDI    __________________________________________________________________________    191       Me, 2.3            0 Me, 6.7                 24.sup.a                    ≈0.5                       10.9/27.3                             134    192       Me, 1.4            0 Me. 1.1                 48 3.94                        2.7/7.84                             114 77000                                     56400                                         1.4.sup.b    193       Me, 2.0            FOA, .74                 24 27.5                        0.80/11.58                             110    194       Me, 2.0            FOA, 1.3                 24 20.7                        0.80/11.58                             126    195       H, 2.0            FOA, .74                 24 1.49                       0.31/4.85                             144    196       2.0.sup.c            FOA, .74                 24 2.00                        0.71/10.73                             135    __________________________________________________________________________     .sup.a Final 3 h at 50° C.     .sup.b THF, PMMA standards.     .sup.c Catalyst is { (2,6i-PrPh)DABAn!PdCH.sub.2 CH.sub.2 CH.sub.2     C(O)OCH.sub.2 (CF.sub.2).sub.6 CF.sub.3)}BAF.sup.

Examples 197-203

In Examples 197-203, structures of the type represented by (VI) and (IX)are described.

Example 197 { (2.6-i-PrPh)₂ DABMe₂ !PdMe(H₂ C═CH₂)}BAF⁻ and {(2.6-i-PrPh)₂ DABMe₂ !Pd(P)H₂ C═CH₂)}BAF⁻

In a drybox under an argon atmosphere, a NMR tube was charged with ˜0.01mmol of ({ (2,6-i-PrPh)₂ DABMe₂ !PdMe}₂ (μ-Cl))BAF⁻ / (Na(OEt₂)₂ BAF orNaBAF! or { (2,6-i-PrPh)₂ DABMe₂ !PdMe(OEt₂)}BAF⁻. The tube was thencapped with a septum, removed from the drybox, and cooled to -78° C. Viagastight syringe, 700 μL of CD₂ Cl₂ was then added to the NMR tube andthe septum was wrapped with Parafilm. The tube was shaken very brieflyin order to dissolve the palladium complex. After acquiring a spectrumat -80° C., 1-10 equiv of olefin was added to the -78° C. solution viagastight syringe, ant the olefin was dissolved in the solution bybriefly shaking the NMR tube. The tube was then transferred to the coldNMR probe and spectra were acquired. Thisolefin complex was preparedfrom both precursors using one equiv of ethylene: ¹ H NMR (CD₂ Cl₂, 400MHz, -60° C.) δ7.72 (s, 8, BAF: C_(o)), 7.54 (s, 4, BAF: C_(p)), 7.4-7.0 (m, 6, H_(aryl)), 4.40 (s, 4, H₂ C═CH₂), 3.38 (br m, 4, O(CH₂CH₃)₂), 2.69 (septet, 2, J =6.73, CHMe₂), 2.63 (septet, 2, J=6.80,C'HMe₂), 2.34 and 2.23 (s, 3 each, N═C(Me)--C'(Me)═N), 1.33 (d, 6,J=6.80, C'HMeMe'), 1.25 (d, 6, J=6.50, CHMeMe'), 1.14 (d, 6, J=7.00,CHMeMe'), 1.10 (br m, 6, O(CH₂ CH₃)₂), 1.07 (d, 6, J=6.80, C'HMeMe'),0.18 (PdMe); ¹³ C NMR (CD₂ Cl₂, 100 MHz, -60° C.) δ180.3 and 174.7(N═C--C'═N), 161.5 (q, J_(BC) =49.6, BAF: C_(ipso)), 143.3 and141.7 (Ar,Ar': C_(ipso)) 134.4 (BAF: C_(o)), 128.6 (Ar: C_(p)), 128.4 (q, J_(BC)=32.3, BAF: C_(m)), 127.7 (Ar': C_(p)), 124.7 and 124.4 (Ar, Ar':C_(o)), 117.3 (BAF: C_(p)), 91.7 (J_(CH) =160.7, H₂ C═CH₂), 65.8 (O(CH₂CH₃)₂), 28.9 (CHMe₂), 28.8 (C'HMe₂), 24.1, 23.4, 22.9 and 22.7 (CHMeMe',C'HMeMe'), 21.7 and 21.5 (N═C(Me)═C'(Me)═N), 15.0 (OCH₂ CH₃)₂), 4.3(PdMe).

In the presence of 5 equiv of ethylene, chain growth was observed at-35° C. Spectral data for { (2,6-i-PrPh)₂ DABMe₂ !Pd(P)(CH₂ ═CH₂)}BAF⁻wherein P is as defined for (VI)! intermediates (CD₂ Cl₂, 400 MHz, -35°C.) are reported in the following table:

    ______________________________________    { (2,6-i-PrPh).sub.2 DABMe.sub.2 !Pd (CH.sub.2).sub.n CH.sub.3 !(H.sub.2    C═CH.sub.2 }.sup.+ BAF.sup.-    H.sub.2 C═CH.sub.2              N═C(Me)--C'(Me)═N                               Pd(CH.sub.2).sub.n Me    n   mult.  δ                      mult. δ                                 mult.                                      δ                                           mult  J    δ    ______________________________________    0   s      4.42   s     2.35 s    2.24 s          0.22    2   s      4.36   s     2.37 s    2.22 t     7.00 0.39    4   s      4.36   s     2.37 s    2.22 t     7.20 0.62    ______________________________________

Addition of 15 more equiv of ethylene and warming to room temperatureleadsto complete consumption of ethylene and the observance of a singleorganometallic species: ¹ H NMR (CD₂ Cl₂, 400 MHz, 24.0° C.) δ7.74 (s,8, BAF: C_(o)), 7.19 (s, 4, BAF: H_(p)), 2.85 (br m, 4, CHMe₂, C'HMe₂),2.36 and 2.23 (s, 3 each, N═C(Me)--C'(Me)═N), 1.5-1.0 (CHMeMe',C'HMeMe'), 1.29 (Pd(CH₂)_(n) CH₃), 0.89 (Pd(CH₂)_(n) CH₃).

Example 198 { (2,6-i-PrPh)₂ DABH₂ !PdMe(H₂ C═CH₂)}BAF⁻ and {(2,6-i-PrPh)₂ DABH₂ !Pd(P)(H₂ C═CH₂)}BAF⁻

This olefin complex, { (2,6-i-PrPh)₂ DABH₂ !PdMe(H₂ C═CH₂)}BAF⁻, wasprepared following the procedure of example197 by both of the analogoussynthetic routes used in example 197, using one equiv of ethylene: ¹ HNMR (CD₂ Cl₂, 400 MHz, -60° C.) δ8.42 and 8.26 (s, 1 each,N═C(H)--C'(H)═N),7.72 (6, 8, BAF: H_(o)), 7.54 (s, 4, BAF: H_(p)),7.42-7.29 (m, 6, H_(aryl)), 4.60 (s, H₂ C═CH₂), 3.37 (q, 4, J=7.03,(O(CH₂ CH₃)₂), 2.89 (septet, 2, J=6.71, CHMe₂), 2.76 (septet, 2, J=6.68,C'HMe₂), 1.35 (d, 6, J=6.72, C'HMeMe'), 1.29 (d, 6, J=6.79, CHMeMe'),1.15 (d, 6, J=6.72,CHMeMe'), 1.09 (d, 6, J=6.54, C'HMeMe'), 1.15 (t, 6,J=7.34, O(CH₂ CH₃)₂), 0.46 (s, 3, PdMe); ¹³ C NMR (CD₂ Cl₂, 400 MHz,-60° C.) δ167.7 (J_(CH) =182, N═C(H)), 162.8 (J_(CH) =182, N═C'(H)),161.4 (q, J=4 9.8, BAF: C_(ipso)), 140.2 and 139.8 (Ar, Ar': C_(ipso)),136.6 and 137.3 (Ar, Ar': C_(o)), 134.4 (BAF: C_(o)), 129.2 and 129.1(Ar, Ar': C_(p)), 128.3 (q, J_(CF) =32.2, BAF: C_(m)), 124.3 and 124.0(Ar, Ar': C_(m)), 124.2 (q, J_(CF) =272.5; BAF: CF₃), 117.3 (BAF:C_(p)), 92.7 (J_(CH) =162.5, H₂ C═CH₂), 65.8 (O(CH₂ CH₃)₂), 28.9 and28.7 (CHMe₂ and C'HMe₂), 25.1, 24.0, 22.0 and 21.9 (CHMeMe', C'HMeMe'),15.12 (J_(CH) =139.2, PdMe), 15.09 (O(CH₂ CH₃)₂).

In the presence of 10 equiv of ethylene, chain growth was monitored at-35° C. Diagnostic ¹ H NMR spectral data (CD₂ Cl₂, 400 MHz, -35° C.) forthe second title compound are reported in thefollowing table:

    ______________________________________    { (2,6-i-PrPh).sub.2 DABH.sub.2 !Pd (CH.sub.2).sub.n CH.sub.3 !(H.sub.2    C═CH.sub.2 }.sup.+ BAF.sup.-    N═C(H)--C'(H)═N                     H.sub.2 C═CH.sub.2                               Pd(CH.sub.2).sub.n Me    n    mult.  δ                       mult.                            δ                                 mult.                                      δ                                           mult  J    δ    ______________________________________    0.sup.a         s      8.42   s    8.27 br s 4.6  s          0.50    2.sup.b         s      8.41   s    8.24 br s 4.6  t     7.85 0.36    4.sup.         s      8.41   s    8.24 br s 4.6  t     7.15 0.62    6.sup.         s      8.41   s    8.24 br s 4.6  t     7.25 0.76    >6   s      8.41   s    8.24 br s.sup.c                                      4.6  m          0.85.sup.d    ______________________________________     .sup.a For n = 0: δ 2.91 and 2.71 (septet, 2 each, CHMe.sub.2,     C'HMe.sub.2), 1.38, 1.32, 1.18 and 1.12 (d, 6 each, CHMeMe', C'HMeMe').     .sup.b For n > 0: δ 2.91 and 2.71 (septet, 2 each, CHMe.sub.2,     C'HMe.sub.2), 1.37 1.35, 1.16 and 1.11 (d, 6 each, CHMeMe', C'HMeMe').     .sup.c In the absence of free ethylene, bound ethylene appears as a sharp     singlet as 4.56 ppm.     .sup.d δ 1.27 (Pd(CH.sub.2).sub.n CH.sub.3).

After the ethylene was consumed at -35° C., the sample was cooled to-95° C. Broad upfield multiplets were observed at -7.2 to -7.5 ppm and-8.0 to -8.5 ppm. The sample was then warmed to room temperature andaspectrum was acquired. No olefins were detected, the upfield multipletswere no longer observable, and a single organometallic species waspresent: ¹ H NMR (CD₂ Cl₂, 400 MHz, 19.8° C.) δ8.41 and 8.28 (s, 1 each,N═C(H)--C'(H)═N), 7.72 (s, 8, BAF: H_(o)), 7.56 (s, 4, BAF: Hp), 3.09(m, 4, CHMe₂, C'HMe₂),1.35, 1.32, 1.26 and 1.22 (d, 6 each, J=6.5-6.8,CHMeMe', C'HMeMe'), 1.27 (Pd(CH₂)_(n) CH₃), 0.88 (Pd(CH₂)_(n) CH₃).

A second spectrum was acquired 12 minutes later at room temperature.Substantial decomposition of the organometallic species was observed.

Example 199 { (2,6-i-PrPh)₂ DABH₂ !PdMe(H₂ C═CH₂)}BAF⁻

This olefin complex, { (2,6-MePh)₂ DABH₂ !PdMe (H₂ C═CH₂)}BAF⁻, wasprepared following the procedure in example197, using { (2,6-MePh)₂DABH₂ !PdMe(OEt₂)}BAF⁻ and oneequiv of ethylene: ¹ H NMR (CD₂ Cl₂, 300MHz, -70° C.) δ8.46 and 8.31 (s, 1 each, N═C(H)--C'(H)═N), 7.72 (s,8,BAF: H_(o)), 7.52 (s, 4, BAF: H_(p)), 7.4-6.4 (m, 6, H_(aryl)), 4.56(s, 4, H₂ C═CH₂), 2.19 and 2.16 (s, 6 each, Ar, Ar': Me), 0.31 (s, 3,PdMe).

In the presence of 10 equiv of ethylene (eq 3), olefin insertion wasmonitored at -30° C. and the production of cis- and trans-2-buteneswasobserved.

Example 200 { (2,6-i-PrPh)₂ DABMe₂ !PdMe(H₂ C═CHMe)}BAF⁻

This olefin complex, { (2,6-i-PrPh)₂ DABMe₂ !PdMe (H₂ C═CHMe)}BAF, wasprepared following the procedure of Example 197, using { (2,6-i-PrPh)₂DABMe₂ !PdMe(OEt₂)}BAF⁻ and one equiv of propylene: ¹ H NMR (CD₂ Cl₂,400 MHz, -61° C.) δ7.73 (s, 8, BAF: H_(o)), 7.55 (s, 4, BAF: H_(p)),7.4-7.0 (m, 6, H_(aryl)), 5.00 (m, 1 H₂ C═CHMe), 4.24 (d, 1, J=9.1,HH'C═CHMe), 4.23 (d, 1, J=14.8, HH'C═CHMe), 3.38 (br q, 4, J=6.50,O(CH₂CH₃)₂), 2.84 (septet, 1, J=6.5, Ar: CHMe₂), 2.68 (m, 3, Ar: C'HMe₂ ;Ar': CHMe₂, C'HMe₂), 2.32 and 2.22 (s, 3 each, N═C(Me)--C'(Me)═N), 1.63(d, 3, J=6.40, H₂ C═CHMe), 1.35, 1.30, 1.25, 1.1, 1.1, 1.04 (d, 3 each,J=6.4-6.7, Ar: C'HMeMe'; Ar': CHMeMe', C'HMeMe'), 1.24 and 1.1 (d, 3each, J=6.4, Ar: CHMeMe'), 1.1 (m, 6, O(CH₂ CH₃)₂), 0.28 (PdMe); ¹³ CNMR (CD₂ Cl₂, 100 MHz, -61° C.) δ179.9 and 174.7 (N═C--C'═N), 161.5 (q,J_(BC) =49.7, BAF: C_(ipso)), 138.8, 137.9, 137.8, 137.7, 137.0 and136.9 (Ar: C_(ipso), C_(o), C_(o) '; Ar': C_(ipso), C_(o), C_(o) ');134.4 (BAF: C_(o)), 128.6 and 128.5 (Ar: C_(p), C_(p) '), 128.4 (q,J_(CF) =31.6, BAF: C_(m)), 124.8, 124.7, 124.4 and 124.4 (Ar: C_(m),C_(m) '; Ar': C_(m), C_(m) '), 124.2 (q, J_(CF) =272.5, BAF: CF₃), 117.3(BAF: C_(p)), 116.1 (J_(CH) =155.8, H₂ C═CHMe), 85.6 (J_(CH) =161.4, H₂C═CHMe), 65.8 (O(CH₂ CH₃)₂), 28.9, 28.7, 28.7, 28.7 (Ar: CHMe₂, C'HMe₂ ;Ar': CHMe₂, C'HMe₂), 24.5, 23.9, 23.5, 23.4, 22.9, 22.9, 22.8, 22.2,21.71, 21.65, 20.9 (H₂ C═CHMe; Ar: CHMeMe', C'HMeMe'; Ar': CHMeMe',C'HMeMe', N═C(Me)--C'(Me)═N), 16.9 (J_(CH) =137.5, PdMe), 15.0 (O(CH₂CH₃)₂).

Example 201 { (2,6-i-PrPh)₂ DABH₂ !PdMe(H₂ C═CHMe)}BAF⁻ and {(2,6-i-PrPh)₂ DABH₂ !Pd(P)(H₂ C═CHMe)}BAF⁻

This olefin complex, { (2,6-i-PrPh)₂ DABH₂ !PdMe (H₂ C═CHMe)}BAF⁻, wasprepared following using both of the synthetic routes used in Example197, using one equiv of propylene: ¹ H NMR (CD₂ Cl₂, 400 MHz, -80° C.)δ8.40 and 8.24 (s, 1 each, N═C(H)--C'(H)═N), 7.72 (s, 8, BAF: H_(o)),7.53 (s, 4, BAF: H_(p)), 7.40-7.27 (m, 6, H_(aryl)), 5.41 (br m, H₂C═CHMe), 4.39 (d, 1, J=8.09, HH'C═CHMe), 4.14 (br d, 1, J=15.29,HH'C═CHMe), 3.10 (br m, 1, CHMe₂), 2.87 (overlapping septets, 2, C'HMe₂,C"HMe₂), 2.59 (br septet, 1, C'"HMe₂), 164 (d, J=6.07, H₂ C═CHMe), 1.39and 1.03 (d, 3 each, J=6.4, CHMeMe'), 1.27, 1.27, 1.14 and 1.1 (d, 3each, J=5.9-6.7, C'HMeMe', C"HMeMe'), 1.23 and 1.1 (d, 3 each, J=6.8,C'"HMeMe'), 0.47 (PdMe); ¹³ C NMR (CD₂ Cl₂, 100 MHz, -80° C.) δ167.1(J_(CH) =181.6, N═C(H)), 163.0 (J_(CH) =182.1, N═C'(H)), 161.3 (q,J_(BC) =50.0, BAF: C_(ipso)), 140.5 and 140.0 (Ar, Ar': C_(ipso)),138.5, 138.3, 137.7 and 137.2 (Ar: C_(o), C_(o) '; Ar': C_(o), C_(o) '),134.2 (BAF: C_(o)), 128.9 and 128.8 (Ar, Ar': C_(p)), 128.1 (q, J_(CF)=31.1, BAF: C_(m)), 124.0 (q, J_(CF) =272.5, BAF: CF₃), 124.6, 123.8,123.8 and 123.6 (Ar: C_(m), C_(m) '; Ar': C_(m), C_(m) '), 117.1 (BAF:C_(p)), 116.4 (J_(CH) =160.3, H₂C═CHMe), 85.4 (J_(CH) =159.9, H₂C═CHMe), 65.7 (O(CH₂ CH₃)₂), 29.2, 28.7, 28.5 and 28.0 (Ar: CHMe₂,C'HMe₂ ;Ar': CHMe₂, C'HMe₂), 26.0, 24.4, 24.03, 23.97, 23.7, 21.9, 21.8,21.7 and 21.6 (H₂ C═CHMe; Ar: CHMeMe', C'HMeMe'; Ar': CHMeMe',C'HMeMe'), 16.6 (J_(CH) =142.1, PdMe), 15.0 (O(CH₂ CH₃)₂).

In the presence of 10 equiv of propylene, chain growth was monitored at-20° C., thus enabling { (2,6-i-PrPh)₂ DABH₂ !Pd (CHMeCH₂) Me!(H₂C═CHMe)}BAF⁻, intermediates to be observed (CD₂ Cl₂, 400 MHz, -20° C.):

    __________________________________________________________________________    { (2,6-i-PrPh).sub.2 DABMe.sub.2 !Pd((CHMeCH.sub.2).sub.n Me)(H.sub.2    C═CHMe)}.sup.+ BAF.sup.-    N═CHC'H═N              HH'C═CHMe                       HH'C═CHMe                                C═CHMe                                      (CHMeCH.sub.2).sub.n Me    n  δ          δ              mult                 J  δ                       mult                          J  δ                                mult                                   δ                                      mult                                         J  δ    __________________________________________________________________________    0  8.40          8.26              d  14.4                    4.25                       d  8.6                             4.47                                m  5.45                                      s     0.59    1  8.38          8.24              d  14.4                    3.98                       d  7.4                             4.25                                m  5.55                                      t  7.1                                            0.51    <1 8.39          8.23              d  13.7                    4.07                       d  8.0                             4.41                                m  5.42    __________________________________________________________________________

Example 202

The compound { (2,6-i-PrPh)₂ DABH₂ !PdMe(H₂ C═CHCH₂Me)}BAF⁻ was madeusing both the synthetic methods described in Example 197, except1-butene was used. ¹ H NMR (CD₂ Cl₂, 400 MHz, -75° C.) δ8.44 and 8.28(s, 1 each, N═C(H)--C'(H)═N), 7.74 (s, 8, BAF: C_(o)), 7.56 (s, 4, BAF:C_(p)), 7.5-7.2 (m, 6, H_(aryl)), 5.4 (m, 1, H₂ C═CHCH₂ CH₃), 4.36 (d,1, J=8.2, HH'C═CHCH₂ CH₃), 4.13 (br m, 1, HH'C═CHCH₂ CH₃), 3.14, 2.92,2.92 and 2.62 (m, 1 each, Ar, Ar': CHMe₂, C'HMe₂), 1.95 and 1.65 (m, 1each, H₂ C═CHCHH'CH₃), 1.5-1.0 (d, 3 each, Ar, Ar': CHMeMe', C'HMeMe'),0.60 (s, 3, PdMe).

Isomerization to cis- and trans-2-butene began at -78° C. and wasmonitored at -15° C. along with chain growth. For Pd P! species,formation of the 1-butene complex occurred selectively in the presenceof cis- and trans-2-butene. Consumption of all olefins was observed at20° C.

Examples 203 { (2,6-i-PrPh)₂ DABH₂ !PdMe(CH₃ CH═CHCH₃)}BAF⁻

Experiments involving the reaction of the bispalladium(μ-Cl)compound/NaBAF (as in Example 197) with trans-2-butene and thebispalladium(μ-Cl) compound alone with cis-2-butene led to partialformation of the corresponding olefin complexes. An equilibrium wasobserved between the ether adduct and the olefin adduct when a compoundofthe type { (2,6-i-PrPh)₂ DABH₂ !PdMe(OEt₂)}BAF⁻ was reacted with oneequiv of cis- or trans-2-butene. Addition of excess 2-butene led tocomplete formation of the olefin adduct. Chain growth, which wasmonitored at 0° C. to room temperature, led to complete consumption ofbutenes. Some butene isomerization occurred during the course of theoligomerization and small amounts of β-hydride elimination products(disubstituted internal olefins and trisubstituted olefins) wereobserved. Oligomer methylene and methyl groups were observedat 1.3 and0.8 ppm, respectively. Diagnostic ¹ H NMR spectral data forthe butenecomplexes follows:

{ (2,6-i-PrPh)₂ DABH₂ !PdMe(trans-CH₃ CH═CHCH₃)}BAF⁻. ¹ H NMR (CD₂ Cl₂,400 MHz, -39° C.) δ8.43 and 8.29 (s, 1 each, N═C(H)--C(H)═N), 5.27 and4.72 (m, 1 each, CH₃ CH═C'HCH₃), 0.73 (PdMe); ¹³ C NMR (CD₂ Cl₂, 100MHz, -95° C.) δ166.8 (J_(CH) =181.5, N═C(H)), 163.2 (J_(CH) =179.8,N═C'(H)), 161.2(q, J_(BC) =49.5, BAF: C_(ipso)), 141.3 and 139.9 (Ar,Ar': C_(ipso)), 138.4, 138.2, 138.0 and 137.0 (Ar, Ar': C_(o), C_(o) '),134.0 (BAF: C_(o)), 128.74 and 128.71 (Ar, Ar': C_(p)), 128.0 (q, J_(CF)=31.9, BAF: C_(m)), 125.4 (J_(CH) =150.0, free MeCH═CHMe), 123.8 (q,J_(CF) =272.5, BAF: CF₃), 124.8, 123.7, 123.5 and 123.4 (Ar, Ar': C_(o),C_(o) '), 117.0 (BAF: C_(p)), 107.0and 106.8 (J_(CH) ˜152, MeCH═C'HMe),65.6 (free O(CH₂ CH₃)₂), 29.5, 28.3, 27.6, 26.5, 24.1, 23.8, 23.6, 21.5,21.3, 21.2, 20.4, 19.9, 19.6, 17.9, 17.5 (Ar, Ar': CHMeMe', C'HMeMe';MeCH═C'HMe), 17.7 (free MeCH═CHMe), 15.0 (PdMe), 14.7 (O(CH₂ CH₃)₂).

{ (2,6-i-PrPh)₂ DABH₂ !PdMe (cis-CH₃ CH═CHCH₃)}BAF⁻. ¹ H NMR (CD₂ Cl₂,400 MHz, -75° C.) δ8.37 and 8.25 (s, 1 each, N═C(H)--C'(H)═N),5.18 (q,2, CH₃ CH═CHCH₃), 1.63 (d, 6, J=4.9, CH₃ CH═CHCH₃), 0.47 (PdMe).

References for the synthesis of bis(oxazoline) ligands and theirtransitionmetal complexes: Corey, E. J.; Imai, N.; Zang, H. Y. J. Am.Chem. Soc. 1991, 113, 728-729. Pfaltz, A. Acc. Chem. Res. 1993, 26,339-345, and references within.

Example 204

2,2-bis{2- 4(S)-methyl-1,3-oxazolinyl!}propane (500 mg, 2.38 mmol) wasdissolved in 10 mL CH₂ Cl₂ in a Schlenk tube under a N₂ atmosphere. Thissolution was added via cannula to a suspension of(1,2-dimethoxyethane)NiBr₂ (647 mg, 2.10 mmol) in 30 mL of CH₂ Cl₂. Thesolution was stirred for 18 hours. The solvent was evaporated underreduced pressure. The product, 2,2-bis{2-4(S)-methyl-1,3-oxazolinyl!}propaneNi(Br₂), was washed with 3×15 mL ofhexane. The product was isolated as a purple powder (0.85 g, 84% yield).

Example 205

The product of Example 204 (14.2 mg, 3.3×10⁻⁵ mol) and toluene (75 mL)were combined in a Schlenk flask under 1 atmosphere ethylene pressure.The solution was cooled to 0° C., and 3.0 mL of a 10% MAO(100 eq)solution in toluene was added. The resulting yellow solution was stirredfor 40 hours. The oligomerization was quenched by the addition of H₂ Oand a small amount of 6M HCl. The organic fraction was separatedfrom theaqueous fraction, and the toluene was removed under reduced pressure. Acolorless oil resulted (0.95 g of oligomer). This illustrates thatpolymerization may be effected by such Pd, Ni and/or Co bisoxazolinecomplexes which are substituted in both 4 positions of the oxazolinering by hydrocarbyl and substituted hydrocarbyl groups.

Example 206 (COD)PdMe(NCMe)!⁺ BAF⁻

To CODPdMeCl (100 mg, 0.37 mmol) was added a solution of acetonitrile(0.08mL, 1.6 mmol) in 25 mL CH₂ Cl₂. To this colorless solution wasadded Na⁺ BAF⁻ (370 mg, 0.4 mmol). A white solid immediatelyprecipitated. The mixture was stirred at -20° C. for 2 hours. Thesolution was concentrated and filtered. Removal of solvent under reducedpressure resulted in a glassy solid. ¹ H NMR (CD₂ Cl₂) δ5.78 (mult, 2H),δ5.42 (mult, 2H), δ2.65 (mult, 4H), δ2.51 (9 mult, 4H), δ2.37 (s, 3H,NCMe), δ1.19 (s, 3H, Pd--Me), δ7.72 (s, 8, BAF⁻, H_(o)), δ7.56 (s, 4,BAF⁻, H_(p)).

Example 207

2,6-(i-Pr)₂ PhDABH₂ !NiBr₂ (10 mg, 1.7×10⁻⁵ mol), toluene (13 mL), and1-hexene (38 mL) were combined in a Schlenk flask under an argonatmosphere. A 10% MAO solution (1.5 mL, 100 eq) in toluene was added toa suspension of the diimine nickel dihalide. The resulting purplesolution was stirred at room temperature for 1 hour. The polymerizationwas quenched and the polymer precipitated from acetone. Theresultingcolorless polymer was dried in vacuo (2.5 g). GPC (toluene, polystyrenestandards) M_(n) =330,000; M_(w) =590,000; M_(n) /M_(w) =1.8.

Example 208

(2,6-i-PrPh)₂ DABH₂ !NiBr₂ (10 mg, 1.7×10⁻⁵ mol)was added to a solutionwhich contained toluene (30 mL) and 1-octene (20 mL). A 10% solution ofMAO (1.5 mL, 100 eq) in toluene was added. The resulting purple solutionwas allowed to stir for 4 hours at room temperature. Solution viscosityincreased over the duration of the polymerization. The polymer wasprecipitated from acetone and dried in vacuo resulting in 5.3 g ofcopolymer. M_(n) =15,200; M_(w) =29,100; M_(w) /M_(n) =1.92.

Example 209

(2,6-i-PrPh)₂ DABMe₂ !Ni(CH₃)₂ (20 mg, 4.1×10⁻⁵ mol) and MAO (35.7 mg,15 eq) were combined as solids in an NMR tube. The solid mixture wascooled to -78° C. and dissolved in 700 μL of CD₂ Cl₂. While cold, 10 μLof etherd¹⁰ was added to stabilize the incipient cation. ¹ H NMRspectrumwere recorded at 253, 273, and 293° K. It was apparent that thestarting nickel dimethyl complex was disappearing and a new nickelcomplex(es) was being formed. Activation of the dimethyl complex wasoccurring through methane loss (s, δ0.22). After 2 hours at 293° K allof the starting species had disappeared. To test for ethylenepolymerization activity, 5000 μL (10 eq) of ethylene was addedvia gastight syringe to the solution at -78° C. The consumption of ethylene wasmonitored by ¹ H NMR spectroscopy. The onset of ethyleneuptake wasobserved at 223° K and all of the ethylene was consumed upon warming theprobe to 293° K. The persistence of the Ni--Me signal during theexperiment suggests that under these conditions propagation is fasterthan initiation. Solid polyethylene was observed upon removing the NMRtube from the probe.

Example 210

(2,6-i-PrPh)₂ DABAn!NiBr₂ (12 mg, 1.7×10⁻⁵ mol) was combined withtoluene (50 mL) and 1-hexene (25 mL) under a N₂ atmosphere. Et₂ AlCl(0.01 mL, 10 eq) was added to the polymerizationmixture. The resultingpurple solution was allowed to stir for 4 hours. After 4 hours thepolymerization was quenched and the polymer precipitatedfrom acetone.The polymerization yielded 2.05 g poly(1-hexene)(731 TO). (GPC, toluene,polystyrene standards) M_(n) =305,000; M_(w) =629,000; M_(w) /M_(n)=2.05. T_(g) =-57° C., T_(m) =52° C. T_(m) =-57° C., T_(g) =-20° C. ¹ HNMR (C₆ D₅ Cl, 142° C.) 10 methyls per 100 carbons. This number issignificantly less than would be expected for strictly atactic 1-hexene.

Example 211

Concentration dependence on catalyst activity in nickel catalyzedpolymerization of α-olefins. A series of homopolymerizations of 1-hexenewere run at 10%, 15%, 20%, 30%, 40%, and 75% 1-hexene by volume. In eachof the above cases 10 mg of (2,6-i-PrPh)₂ DABH₂ !NiBr₂ was taken up intoluene and 1-hexene (50 mL total volume 1-hexene+toluene). All of thepolymerizations were run at 25° C. and activated by the addition of 1.5mL of a 10% MAO solution in toluene. The polymerizations were stirredfor 1 hour and quenched upon the additionof acetone. The polymer wasprecipitated from acetone and dried in vacuo. 10% by volume 1-hexeneyielded 2.5 g poly(1-hexene), 15% by volume 1-hexene yielded 2.6 gpoly(1-hexene), 20% by volume 1-hexene yielded 3.0 g poly(1-hexene), 30%by volume 1-hexene yielded 2.6 g poly(1-hexene), 40%by volume 1-hexeneyielded 2.6 g poly(1-hexene), 75% by volume 1-hexene yielded 2.5 gpoly(1-hexene).

Example 212

FeCl₂ (200 mg, 1.6 mmol) and 20 ml of CH₂ Cl₂ were combined in a Schlenkflask under an argon atmosphere. In a separate flask, 550 mg(2,6-i-PrPh)₂ DABMe₂ and 20 ml CH₂ Cl₂ were combined, resulting in ayellow solution. The ligand solution was slowly (2 hr) transferred viacannula into the suspension of FeCl₂. The resulting solution was stirredat 25° C. After 4 hr. the solution was separated from the unreactedFeCl₂ by filter cannula (some purple solid was also left behind). Thesolvent was removed in vacuo to give a purple solid (0.53 g, 71%yield).A portion of the purple solid was combined with 50 ml of tolueneunder 1 atm of ethylene. The solution was cooled to 0° C., and 6 ml of a10% MAO solution in toluene was added. The mixture was warmed to 25° C.and stirred for 18 hr. The polymer was precipitated by acetone,collected by suction filtration, and washed with 6M HCl, water andacetone. The white polymer was dried under reduced pressure. Yield 13mg.

Example 213

A 58-mg (0.039-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ CH₂C(O)OCH₃ } BAF⁻ was placed in a 600-mL stirred autoclave under nitrogenwith 150 mL of deaerated water. This mixture was pressurized to 5.5 MPawith ethylene and was stirred at 23° C. for 68 hr. When the ethylene wasvented, the autoclave was found to be full ofrubbery polymer: on top wasa layer of white, fluffy elastomeric polyethylene, while beneath wasgray, dense elastomeric polyethylene. The water was poured out of theautoclave; it was a hazy light blue, containing a tiny amount ofemulsified polyethylene; evaporation of the whole aqueous sample yieldeda few mg of material. The product was dried under high vacuum to yield85.5 g of amorphous elastomeric polyethylene, which exhibited a glasstransition temperature of -61° C. and a melting endotherm of -31° C. (16J/g) by differential scanning calorimetry. H-1 NMR analysis (CDCl₃): 105methyl carbons per 1000 methylene carbons. Gel permeation chromatography((trichlorobenzene, 135° C., polystyrene reference, results calculatedas polyethylene using universal calibration theory): M_(n) =42,500;M_(w) =529,000; M_(w) /M_(n) =12.4. This example demonstrates the use ofpure water asa polymerization medium.

Example 214

A 73-mg (0.049 mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ CH₂C(O)OCH₃ }BAF⁻ was placed in a 600-mL stirred autoclave under nitrogenwith 150 mL of deaerated water; to this was added3.1 mL (3.3 g) ofTriton® X-100 nonionic surfactant. This mixture was pressurized to 5.6MPa with ethylene and was stirred at 23° C. for 17 hr. When the ethylenewas vented, most of the emulsion came out the valve due to foaming; itwas caught in a flask. There was polymer suspended in the emulsion; thiswas filtered to give, after MeOH and acetone washing and air-drying, 2.9g of amorphous polyethylene as a fine,gray rubber powder. The filtratefrom the suspended polymer was a clear gray solution; this wasconcentrated on a hot plate to yield recovered Triton® X-100 andpalladium black. There was no polymer in the aqueousphase. Theelastomeric polyethylene product exhibited a glass transitiontemperature of -50° C. and a melting endotherm of 48° C. (5 J/g) bydifferential scanning calorimetry. H-1 NMR analysis (CDCl₃): 90 methylcarbons per 1000 methylene carbons. Gel permeation chromatography(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n) =31,000; M_(w)=311,000; M_(w) /M_(n) =10.0. This example demonstrates the aqueousemulsion polymerization of ethylene in the presence of a non-ionicsurfactant.

Example 215

A 93-mg (0.110-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ CH₂C(O)OCH₃ }⁺ SbF₆ ⁻ was placed in a 600-mL stirred autoclave undernitrogen with 150 mL of deaerated water; tothis was added 0.75 g (1.4mmol) of FC-95® anionic fluorosurfactant (potassiumperfluorooctansulfonate). This mixture was pressurized to 5.1 MPa withethylene and was stirred at 23° C. for 15 hr. The ethylenewas vented;the product consisted of polymer suspended in emulsion as well as somepolymer granules on the wall of the autoclave; the emulsion was filteredto give, after MeOH and acetone washing and air-drying, 2.4 g ofamorphous polyethylene as a fine, gray rubber powder. The hazy blue-grayaqueous filtrate was evaporated to yield 0.76 g of residue; hot waterwashing removed the surfactant to leave 0.43 g of dark brown stickypolyethylene rubber. H-1 NMR (CDCl₃) analysis: 98 CH₃ 's per 1000 CH₂'s. Differential scanning calorimetry: melting point: 117° C. (111 J/g);glass transition: -31° C. (second heat; no apparent Tg on first heat).This example demonstrates the aqueous emulsion polymerization ofethylene in the presence of a anionic surfactant. This example alsodemonstrates that a true aqueous emulsion ofpolyethylene can be obtainedby emulsion polymerization of ethylene with these catalysts in thepresence of an appropriate surfactant.

Example 216

A 90-mg (0.106-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂CH₂ CH₂C(O)OCH₃ }⁺ SbF₆ ⁻ was placed in a 600-mL stirred autoclave undernitrogen with 150 ml of deaerated water; tothis was added 0.75 g (2.1mmol) of cetyltrimethylammonium bromide cationicsurfactant. This mixturewas pressurized to 5.2 MPa with ethylene and was stirred for 66 hr at23° C. The ethylene was vented; the product consisted of polymersuspended in a dark solution; this was filtered to give, after MeOH andacetone washing and air-drying, 0.13 g of amorphous polyethylene as atacky, gray rubber powder. There was no polymer in the aqueous phase.H-1 NMR (CDCl₃) analysis: 96 CH₃ 's per 1000 CH₂ 's. Differentialscanning calorimetry: glass transition: -58° C.; melting endotherms:40°, 86°, 120° C.(total: 20 J/g). This example demonstrates the aqueousemulsion polymerization of ethylene in the presence of a cationicsurfactant.

Example 217

An 87-mg (0.103-mmol) sample of { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂C(O)OCH₃ }⁺ SbF₆ ⁻ was placed in a 600-mL stirred autoclave undernitrogen. To this was added 100mL of dry, deaerated methyl acrylatecontaining 100 ppm of phenothiazine asa free-radical polymerizationinhibitor. The autoclave was stirred and pressurized to 300 psig withethylene over 5 min. The autoclave was then pressurized to 600 psig withan additional 300 psig of carbon monoxide (300 psig E+300 psig CO=600psig). The reaction was stirred for 20 hr at 23° C. as the autoclavepressure dropped to 270 psig. The ethylene was then vented; theautoclave contained a yellow solution which was concentrated by rotaryevaporation, taken up in methylene chloride, filtered, and againconcentrated to yield 0.18 g of dark brown viscous oil. The product waswashed with hot acetone to remove the brown catalyst residues and washeld under high vacuum to yield 55 mg of a colorless, viscous liquidterpolymer. The infrared spectrum exhibited carbonyl absorbances at 1743(ester), 1712 (ketone), and 1691 cm⁻¹. H-1 NMR (CDCl₃) analysis: 76CH₃'s per 1000 CH₂ ; there were peaks at 2.3 (t, CH₂ COOR), 2.7 (m, CH₂CO), and 3.66 ppm (COOCH₃). The polymer contained 3.3 mol % MA (9.4 wt %MA). The carbon monoxide content was not quantified, but the absorbancein the infrared spectrum of the polymer due to ketone was about 1/2 to2/3 the absorbance due to acrylate ester. This example demonstrates theuse of carbon monoxide as a monomer.

Example 218

A 20-mg (0.035-mmol) sample of NiBr₂ 2-NpCH═N(CH₂)₃ N═CH-2-Np!, whereNp=naphthyl, (see structure below) was magnetically stirred undernitrogen in a 50-mL Schlenk flask with 25 mL of dry deaerated, toluene.Then 0.6 mL of polymethylalumoxane (3.3M) was injected; the light pinksuspension became a dark gray-green solution, eventually with blackprecipitate. The mixture was immediately pressurizedwith ethylene to 7psig and was stirred at 23° C. for 18 hr, during which time the mixturebecame a clear yellow solution with black, sticky precipitate. Theethylene was vented; the offgas contained about 3% butenes (90:101-butene: trans-2-butene) by gas chromatography (30-m Quadrex GSQ®Megabore column; 50-250° C. at 10°/min). The toluene solution wasstirred with 6N HCl and methanol and was separated; concentration of thetoluene solution followed by acetone rinsing the residue yielded 85 mgof liquid polyethylene. H-1 NMR (CDCl₃) analysis: 209 CH₃ 's per 1000CH₂ 's. This example demonstrates the efficacy of a catalyst with abis-imine ligand in which the imine groups are not alpha to one another.##STR85##

Example 219

A 17-mg (0.027-mmol) sample of (2,6-i-PrPh)₂ DABMe₂ !ZrCl₄ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene. Then 0.6 mL of polymethylalumoxane (3.3M) wasinjected; the yellow suspension became an orange-yellow solution. Themixture was pressurized with ethylene to 7 psig and was stirred at 23°C. for 20 hr, during which time polymer slowly accumulated on the stirbar and eventually rendered the solution unstirrable. Thetoluenesolution was stirred with 6N HCl and methanol and was filtered toyield (after MeOH and acetone washing and air-drying) 1.01 g of white,fluffy polyethylene. Differential scanning calorimetry exhibited amelting point of 131° C. (124 J/g). This example demonstrates theefficacy of a Zr(IV) catalyst bearing a diimine ligand.

Example 220

A 14-mg (0.024-mmol) sample of (2,6-i-PrPh)₂ DABMe₂ !TiCl₄ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deareated toluene (distilled from Na under N₂). Then 0.6 mL ofpolymethylalumoxane (3.3M) was injected; the yellow suspension became adark brown suspension with some precipitate. The mixture was pressurizedwith ethylene to 7 psig and was stirred at 23° C. for 3hr, during whichtime polymer accumulated and rendered the solution unstirrable. Thetoluene solution was stirred with 6N HCl and methanol andwas filtered toyield, after MeOH and acetone washing and air-drying, 1.09 g of white,fluffy polyethylene. Differential scanning calorimetry exhibited amelting point of 131° C. (161 J/g). This example demonstrates theefficacy of a Ti(IV) catalyst bearing a diimine ligand.

Example 221

A 28-mg (0.046-mmol) sample of (2,6-i-PrPh)₂ DABMe₂ !CoBr₂ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene. Then 0.5 mL of polymethylalumoxane (3.3M) wasinjected, resulting in a deep purple solution, and the mixture waspressurized immediately with ethylene to 7 psig and stirred at 23° C.for 17 hr. The solution remained deep purple but developed someviscosity due to polymer. The ethylene was vented; the offgas contained1.5%

1-butene by gas chromatography (30-m Quadrex GSQ® Megabore column;50°-250° C. at 10°/min). The toluene solution was stirred with 6NHCl/methanol and was separated; concentration of the toluene solutionyielded, after drying under high vacuum, 0.18 g of elastomericpolyethylene. A film of polymer cast from chlorobenzene was stretchywith good elastic recovery. Differential scanning calorimetry: glasstransition: -41° C.; melting endotherm: 43° C. (15 J/g). This exampledemonstrates the efficacy of a cobalt (II) catalyst bearing a diimineligand.

Example 222

A 35-mg (0.066-mmol) sample of (2,6-i-PrPh)₂ DABMe₂ !FeCl₂ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry, deaerated toluene. Then 0.6 mL of polymethylalumoxane (3.3M) wasinjected; the deep purple-blue solution became a royal purple solution,which evolved to deep green-black over time. The mixture was immediatelypressurized with ethylene to 7 psig and was stirred at 23° C. for 70 hr,during which time the mixture became a pale greensolution with black,sticky precipitate. The ethylene was vented; the toluene solution wasstirred with 6N HCl and methanol and was filtered to yield 90 mg ofpolyethylene.

Differential scanning calorimetry: melting endotherm: 128° C. (84 J/g).This example demonstrates the efficacy of a iron (II) catalyst bearing adiimine ligand.

Example 223

A mixture of 3.2 g of the polyethylene product of Example 96, 60 mg (1.9wt%) of dicumyl peroxide, and 50 g (1.6 wt %) of triallylisocyanurate(TAIC) was dissolved in 100 mL of THF. The polymer was precipitated bystirring the solution in a blender with water; the peroxide and TAIC arepresumed to have stayed in the polymer. The polymer was pressed into aclear, rubbery, stretchy film at 125° C. Strips of this film weresubsequently pressed at various temperatures (100° C., 150° C., 175° C.,200° C.) for various times (1 min, 5 min, 10 min) to effectperoxide-induced free-radical crosslinking. The cured sheets were allclear and stretchy and shorter-breaking: 100° C. for 10 min gave noapparent cure, while 150° C./5 min seemed optimal. The cured films camecloser to recovering their original dimensions than the uncured films.This example demonstrates peroxide curing of the amorphous elastomericpolyethylene.

Example 224

A 28-mg (0.050-mmol) sample of TiCl₄ 2-NpCH═N(CH₂)₂ N═CH-2-Np!, whereNp=naphthyl, (see structure below) was magnetically stirred undernitrogen in a 50-mL Schlenk flask with 25 mL of dry, deaerated toluene.Then 0.6 mL of polymethylalumoxane (3.3M) was injected;the orangesuspension became reddish-brown. The mixture was immediately pressurizedwith ethylene to 7 psig and was stirred at 23° C. for 66 hr. The toluenesolution was stirred with 6N HCl and methanol and was filtered to yield,after methanol washing and air-drying, 1.30 g of white,fluffypolyethylene.

Differential scanning calorimetry: melting endotherm: 135° C. (242 J/g)

This example demonstrates the efficacy of a catalyst with a bis-imineligand in which the imine groups are not alpha to one another. ##STR86##

Example 225

A 33-mg (0.053-mmol) sample of (2,6-i-PrPh)₂ DABMe₂ !ScCl₃ -THF wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with25 mLof dry, deaerated toluene. Then 0.6 mL of polymethylalumoxane (3.3M) wasinjected; the pale orange solution became bright yellow. The mixture wasimmediately pressurized with ethylene to 7 psig and was stirred at 23°C. for 17 hr, during which time the mixture remained yellow andgranularsuspended polymer appeared. The ethylene was vented; the toluenesolution was stirred with 6N HCl and methanol and was filtered to yield2.77 g of white, granular polyethylene. This example demonstrates theefficacy of a scandium (III) catalyst bearing a diimine ligand.

Example 226 (2-t-BuPh) 2DABAN

This compound was made by a procedure similar to that of Example 25.Three mL (19.2 mmol) of 2-t-butylaniline and 1.71 g (9.39 mmol) ofacenaphthenequinone were partially dissolved in 50 mL of methanol(acenaphthenequinone was not completely soluble). An orange product wascrystallized from CH2Cl2 (3.51 g, 84.1%). 1H NMR (CDCl3, 250 MHz)d 7.85(d, 2H, J=8.0 Hz, BIAN: Hp), 7.52 (m, 2H, Ar: Hm), 7.35 (dd, 2H, J=8.0,7.3 Hz, BIAN: Hm), 7.21 (m, 4H, Ar: Hm and Hp), 6.92 (m, 2H, Ar: Ho),6.81(d, 2H, J=6.9 Hz, BIAN: Ho), 1.38 (s, 18H, C(CH3)3).

Example 227

Methyl vinyl ketone was stirred over anhydrous K₂ CO₃ and vacuumtransferred on a high vacuum line to a dry flask containingphenothiazine (50 ppm). Ethylene and methyl vinyl ketone (5 ml) werecopolymerized according to Example 16 using catalyst { (2,6-i-PrPh)₂DABMe₂ ! PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺ SbF₆ ⁻ (0.084 g, 0.10 mmol) to give0.46 g copolymer (0.38 g after correcting for catalyst residue). ¹ H-NMR(CDCl₃): 0.75-0.95(m, CH₃); 0.95-1.45(m, CH and CH₂); 1.55(m, --CH₂ CH₂C(O)CH₃); 2.15(s, --CH₂ CH₂ C(O)CH₃); 2.4(t, --CH₂ CH₂ C(O)CH₃). Basedon the triplet at 2.15, it appears that much of the ketone functionalityis located on the ends of hydrocarbon branches. Integration shows thatthe copolymer contains 2.1 mole % methyl vinyl ketone, and 94 methylcarbons (exclusive of methyl ketones) per 1000 methylene carbons. Theturnover numbers are 128 equivalents of ethylene and 3 equivalents ofmethyl vinyl ketone per Pd. GPC (THF, PMMA standard):Mn=5360 Mw=7470Mw/Mn=1.39.

Example 228

A Schlenk flask containing 122 mg (0.0946 mmol) of { (4-MePh)₂ DABMe₂!PdMe(N.tbd.CMe)}⁺ BAF⁻ was placed under a CO atmosphere. The yellowpowder turned orange upon addition of CO, and subsequent addition of 20mL of CH₂ Cl₂ resulted in the formation of a clear red solution.t-Butylstyrene (10 mL) was added next and the resulting orange solutionwas stirred for 25.7 h at room temperature. The solution was then addedto methanol in order to precipitate the polymer, which was collected byfiltration and dried in a vacuum oven at 50° C. overnight (yield=4.03g): GPC Analysis (THF, polystyrene standards) M_(w) =8,212; M_(n)=4,603; PDI=1.78. The ¹ H NMR spectrum (CDCl₃, 400 MHz) of the isolatedpolymer was consistent with a mixture of copolymer andpoly(t-butylstyrene).

Mixtures of alternating copolymer and poly(t-butylstyrene) were obtainedfrom this and the following polymerizations and were separated byextraction of the homopolymer with petroleum ether. When R² and R⁵ were4-MePh (this example) atactic alternating copolymer was isolated. WhenR² and R⁵ were 2,6-i-PrPh (Example 229) predominantly syndiotacticalternating copolymer was isolated. (Spectroscopic data for atactic,syndiotactic, and isotactic t-butylstyrene/CO alternating copolymers hasbeen reported: M. Brookhart, et al., J. Am. Chem. Soc. 1992, 114,5894-5895; M. Brookhart, et al., J. Am. Chem. Soc. 1994, 116,3641-3642.)

Petroleum ether (˜200 mL) was added to the polymer mixture in order toextract the homopolymer, and the resulting suspension was stirredvigorously for several h. The suspension was allowed to settle, and thepetroleum ether solution was decanted off of the gray powder. The powderwas dissolved in CH₂ Cl₂ and the resulting solution was filteredthroughCelite. The CH₂ Cl₂ was then removed and the light gray powder (0.61 g)was dried in vacuo. ¹ H and ¹³ C NMR spectroscopic data are consistentwith the isolation of atactic alternating copolymer: ¹ H NMR (CDCl₃, 300MHz) δ7.6-6.2 (br envelope, 4, H_(aryl)), 4.05 and 3.91 (br, 1, CHAr'),3.12 and 2.62 (br, 2, CH₂), 1.26-1.22 (br envelope, 9, CMe₃); ¹³ C NMR(CDCl₃, 75 MHz) δ207.5-206.0 (br envelope, --C(O)--), 150.0-149.0 (br,Ar': C_(p)), 135.0-133.8 (br envelope, Ar': C_(ipso))127.9 (Ar': C_(m)),126.0-125.0 (br, Ar': C_(o)), 53.0-51.0 (br envelope, CHAr'), 46.0-42.0(br envelope, CH₂), 34.3 (CMe₃), 31.3 (CMe₃).

Example 229

The procedure of Example 228 was followed using 134 mg (0.102 mmol) {(2,6-i-PrPh)₂ DABMe₂ !PdMe(N.tbd.CMe)}⁺ BAF⁻. A mixture (2.47 g) ofcopolymer and poly(t-butylstyrene) was isolated. GPC Analysis (THF,polystyrene standards): M_(w) =10,135; M_(n) =4,922; PDI=2.06. Followingthe extraction of the homopolymer with petroleum ether, 0.49 g ofoff-white powder was isolated. ¹ H and ¹³ C NMRspectroscopic data areconsistent with the isolation of predominantly syndiotactic copolymer,although minor resonances are present: ¹ H NMR (CDCl₃, 300 MHz) δ7.20(d, 2, J=8.14, Ar': H_(o) or H_(m)), 6.87 (d, 2, J=7.94, Ar': H_(o) orH_(m)), 3.91 (dd, 1, J=9.06, 3.16, CHAr'), 3.15 (dd, 1, J=18.02, 9.96,CHH'), 2.65 (dd, 1, J=17.90, CHH'), 1.25 (s, 9, CMe₃); ¹³ C NMR (CDCl₃,75 MHz) δ207.0 (--C(O)--), 149.8 (Ar': C_(p)), 134.5 (Ar': C_(ipso)),127.8 (Ar': C_(m)), 125.6 (Ar': C_(o)), 51.7 (CHAr'), 45.6 (CH₂),34.3(CMe₃), 31.3 (CMe₃).

Example 230

A Schlenk flask containing 74.3 mg (0.0508 mmol) of { (2,6-i-PrPh)₂DABMe₂ !PdMe(OEt₂)}⁺ BAF⁻ was evacuated, cooled to -78° C. and thenplaced under an atmosphere of ethylene/CO (1:1 mixture). Following theaddition of 50 mL of chlorobenzene, the reaction mixture was allowed towarm to room temperature and stirred. A small amount of whiteprecipitate appeared on the sides of the flask after 0.5 hand moreprecipitate formed during the next two days. After stirring for 47.2 h,the reaction mixture was added to methanol and the resulting suspensionwas stirred. The precipitate was then allowed to settle, and themethanol was decanted, leaving behind a cream powder (0.68 g), which wasdried in a vacuum oven at 70° C. for one day. ¹ H and ¹³ C NMRspectroscopic data are consistent with the isolation of an alternatingcopolymer of ethylene and carbon monoxide: ¹ H NMR (CDCl₃/pentafluorophenol, 400 MHz) δ2.89 (--C(O)--CH₂ CH₂ --C(O)--); ¹³ C NMR(CDCl₃ /pentafluorophenol, 100 MHz) δ212.1 (--C(O)--), 35.94 (CH₂).

For comparisons of the spectroscopic data of alternating E/CO copolymersherein with literature values, see for example: E. Drent, et al., J.Organomet. Chem. 1991, 417, 235-251.

Example 231

A Schlenk flask containing 73.2 mg (0.0500 mmol) of { (2,6-i-PrPh)₂DABMe₂ !PdMe(OEt₂)}⁺ BAF⁻ was evacuated, cooled to -78° C., and thenback-filled with ethylene (1 atm). Chlorobenzene (50 mL) was added viasyringe and the solution was allowed to warm to roomtemperature. After0.5 h, the reaction vessel was very warm and ethylene was being rapidlyconsumed. The reaction flask was then placed in a room-temperature waterbath and stirring was continued for a total of 3 h.A very viscoussolution formed. The atmosphere was then switched to ethylene/carbonmonoxide (1:1 mixture, 1 atm) and the reaction mixture wasstirred for47.7 more hours. During this time, the solution became slightlymoreviscous. The polymer was then precipitated by adding thechlorobenzenesolution to methanol. The methanol was decanted off of thepolymer, which was then partially dissolved in a mixture of Et₂ O, CH₂Cl₂and THF. The insoluble polymer fraction (2.71 g) was collected on asintered glass frit, washed with chloroform, and then dried in a vacuumoven at 70° C. for 12 h. The NMR spectroscopic data of the gray rubberymaterial are consistent with the formation of a diblock of branchedpolyethylene and linear poly(ethylene-carbon monoxide): ¹ H NMR (CDCl₃/pentafluorophenol, 400 MHz) δ2.85 (--C(O)CH₂ CH₂ C(O)--), 2.77(--C(O)CH₂, minor), 1.24 (CH₂), 0.83 (CH₃); Polyethylene BlockBranching: ˜103 CH₃ per 1000 CH₂ ; Relative Block Length (CH₂ CH₂)_(n)--(C(O)CH₂CH₂)_(m) !: n/m=2.0. ¹³ C NMR (CDCl₃ /pentafluorophenol, 100MHz; data for ethylene-CO block) δ211.6 (--C(O)--), 211.5 (--C(O)--,minor), 35.9 (C(O)--CH₂ CH₂ --C(O)), 35.8 (C(O)CH₂, minor).

Example 232

A Schlenk flask containing 75.7 mg (0.0527 mmol) of { (2,6-i-PrPh)₂DABH₂ !PdMe(OEt₂)}⁺ BAF⁻ was evacuated, cooled to -78° C., and thenback-filled with ethylene (1 atm). Chlorobenzene (50 mL) was added viasyringe, the solution was allowed to warm to room temperature andstirred for 3 h. The solution did not become warm or viscous during thistime. The atmosphere was changed to ethylene/carbon monoxide (1:1mixture, 1 atm) and the solution was stirred for 47.7 more hours. Duringthis time, the reaction mixture became quite viscous and solvent-swollenpolymer precipitated on the sides of the flask. The polymer wasprecipitated by addition of the reaction mixture to methanol. Themethanol was decanted off of the rubbery polymer (4.17 g), which wasthen dried in a vacuum oven for one day at 70° C. Chloroform was thenadded to the polymer and the rubbery insoluble fraction (0.80 g) wascollected on a sintered glass frit. A ¹ H NMR spectrum (CDCl₃, 400 MHz)of the chloroform-soluble polymer showed no carbon monoxideincorporation; only branched polyethylene was observed. NMRspectroscopic data for the chloroform-insoluble fraction was consistentwith the formation of a diblock of branched polyethylene and linearpoly(ethylene-carbon monoxide): ¹ H NMR (CDCl₃ /pentafluorophenol, 400MHz) δ2.88 (C(O)CH₂ CH₂ C(O)), 1.23 (CH₂), 0.83 (CH₃); PolyethyleneBlock Branching: 132 CH₃ per 1000 CH₂ ; Relative Block Length (CH₂CH₂)_(n) --(C(O)CH₂ CH₂)_(m) !: n/m=0.30; ¹³ C NMR(CD₂ Cl₂/pentafluorophenol, 100 MHz; data for ethylene-CO block) δ211.3(--C(O)--), 211.3 (--C(O)--, minor), 36.5 (--C(O)CH₂ CH₂ C(O)--), 36.4(C(O)CH₂, minor).

Example 233

A 34-mg (0.053-mmol) sample of the crude product of Example 235, wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLofdry, deaerated toluene. Then 0.6 mL of polymethylalumoxane (3.3M) wasinjected; the purple-pink suspension became a gold-green solution withblack precipitate. The mixture was pressurized with ethylene to 152 kPa(absolute) and was stirred for 20 hr. Within the first hour, polymer wasobserved to be accumulating on the stir bar and the walls of the flask.The ethylene was vented and the toluene solution was stirred with 6N HCland methanol and was filtered to yield (after MeOH and acetone washingandair-drying) 1.37 g of white, granular polyethylene. This exampledemonstrates the efficacy of a catalyst with a 1,3-diimine ligand.

Example 234 Synthesis of MeC(═N-2,6-C₆ H₃ -iPr₂)CH═C(NH-2,6-C₆ H₃-iPr₂)Me

Concentrated HCl (0.3 ml, 3.6 mmol) was added to a solution of2,4-pentanedione (1.2 g, 12 mmol) and 2,6-diisopropylaniline (5.0 ml,26.6mmol) in 15 ml ethanol. The reaction mixture was refluxed for 21 hduring which time a white solid precipitated. This was separated byfiltration, dried under vacuum and treated with saturated aqueous sodiumbicarbonate. The product was extracted with methylene chloride, and theorganic layer dried over anhydrous sodium sulfate. Removal of thesolvent afforded 1.43 g (28%) of the title compound as a whitecrystalline product; mp: 140°-142° C.; ¹ -H NMR: (CDCl₃) δ12.12 (bs, 1H,NH), 7.12 (m, 6H, aromatic), 4.84 (s, 1H, C═CH--C), 3.10 (m, 4H,isopropyl CH, J=7 Hz), 1.72 (s, 6H, CH₃), 1.22 (d, 12H, isopropyl CH₃,J=7 Hz), 1.12 (d, 12H, isopropyl CH₃, J=7 Hz). ¹³ C NMR: (CDCl₃) δ161.36(C═N), 142.63 (aromatic C-1), 140.89 (aromatic C-2), 125.27 (aromaticC-4), 123.21 (aromatic C-3), 93.41 (--CH═), 28.43 (isopropyl CH), 24.49(isopropyl CH₃), 23.44 (isopropyl CH₃), 21.02 (CH₃). MS: m/z=418.333(calc. 418.335).

Example 235 Synthesis of an ethylene polymerization catalyst fromNi(MeOCH₂ CH₂ OMe)Br₂ and MeC(═N-2,6-C₆ H₃ -iPr₂)CH═C(NH-2,6-C₆ H₃-iPr₂)Me

Ni(MeOCH₂ CH₂ OMe)Br₂ (0.110 g, 0.356 mmol) and MeC(═N-2,6-C₆ H₃-iPr₂)CH═C(NH--C₆ H₃ -iPr₂)Me (0.150 g, 0.359 mmol) were combined in 10mL of methylene chloride to give a peach-colored suspension. Thereaction mixture was stirred at room temperature overnight, during whichtime a lavender-colored powder precipitated. This was isolated byfiltration, washed with petroleum ether and dried affording 0.173 g ofmaterial. This compound was used as the catalyst in Example 233.

Example 236 { (2,6-i-PrPh)₂ DABMe₂ !Pd(MeCN)₂ }(BF₄)₂

Pd(MeCN)₄ !(BF₄)₂ (0.423 g, 0.952 mmol) and (2,6-i-PrPh)₂ DABMe2 (0.385g, 0.951 mmol) were dissolved in 30 mL acetonitrile under nitrogen togive an orange solution. The reaction mixture was stirred at roomtemperature overnight; it was then concentrated in vacuo to afford ayellow powder. Recrystallization from methylene chloride/petroleum etherat -40° C. afforded 0.63 g of the title compound as a yellow crystallinesolid. 1H NMR (CD₂ Cl₂) δ7.51 (t, 2H, H_(para)), 7.34 (d, 4H, H_(meta)),3.22 (sept, 4H, CHMe₂), 2.52 (s, 6H, N═CMe), 1.95 (s, 6H, NC.tbd.Me),1.49 (d, 12H, CHMe₂), 1.31 (d, 12H, CHMe₂).

Example 237 Ethylene Polymerization Catalyzed by { (2,6-i-PrPh)₂ DABMe₂!Pd(MeCN)₂ }(BF₄)₂

A 100 mL autoclave was charged with a solution of { (2,6-i-PrPh)₂ DABMe₂!Pd(MeCN)₂ }(BF₄)₂ (0.043 g, 0.056 mmol) dissolved in 50 mL chloroformand ethylene (2.8 MPa). The reaction mixturewas stirred under 2.8 MPaethylene for 9 h 15 min. During this time, the temperature inside thereactor increased from 23° to 27° C. The ethylene pressure was thenvented and volatiles removed from the reaction mixture to afford 1.65 gof a viscous yellow oil. This was shown by ¹ H NMR to be branchedpolyethylene containing 94 methyl-ended branches per 1000 methylenes.

Example 238 Ethylene polymerization by Ni(COD)₂ /(2,6-i-PrPh)₂DABMe₂.HBAF(Et₂ O)₂

Ni(COD)₂ (0.017 g, 0.06 mmol) and (2,6-i-PrPh)₂ DABMe₂.HBAF(Et₂ O)₂(0.085 g, 0.06 mmol) were dissolved in 5 mL of benzene under nitrogen atroom temperature. The resulting solutionwas quickly frozen, and thenallowed to thaw under 6.9 MPa of ethylene at 50° C. The reaction mixturewas agitated under these conditions for18 h affording a solvent swelledpolymer. Drying afforded 5.8 g of a polyethylene as a tough, rubberymaterial.

Example 239 Ethylene polymerization by Pd₂ (dba)₃(dba=dibenzylideneacetone)/(2,6-i-PrPh)₂ DABMe₂.HBAF(Et₂ O)₂

A sample of (Et₂ O) HBAF (200 mg, 0.20 mmol) was dissolved in 10 mLofEt₂ O. To this solution was added 1 equivalent of DABMe₂ (or otherα-diimine). The solution became red. Removal of the volatiles in vacuogave a red solid of the acid-α-diimine complex.

Pd₂ (dba)₃ (0.054 g, 0.06 mmol) and (2,6-i-PrPh)₂ DABMe₂.HBAF(Et₂ O)₂(0.076 g, 0.05 mmol) were dissolved in 5 mL of benzene under nitrogen atroom temperature. The resulting solutionwas agitated under 6.9 MPa ofethylene at 50° C. for 18 h. The product mixture was concentrated todryness in vacuo, affording an extremely viscous oil. ¹ H NMR showed theproduct to be branched polyethylene containing 105 methyl ended branchesper 1000 methylenes.

Example 240

Toluene (30 mL), 4-vinylcyclohexene (15 mL), and 20 mg of (2,6-i-PrPh)₂DABH₂ !NiBr₂ (0.03 mmol) were combined in a Schlenk flask under anatmosphere of ethylene. A 10% MAO solution (3 mL) in toluene was added.The resulting purple solution was stirred for 16 h. After only a fewhours, polymer began to precipitate and adhere to the walls of theflask. The polymerization was quenched and the polymer precipitated fromacetone. The polymer was dried in vacuo overnight resulting in 100 mg ofa white solid. Characterization by proton NMR suggests in corporation of4-vinylcyclohexene as a comonomer. ¹ H NMR(CDCl₃) δ5.64 (m, vinyl,cyclohexene), 2.0-0.9 (overlapping m, including cyclohexyl methylene,methylene (PE), methine), 0.78 (methyl, PE). There are also some minorsignals in the base line that suggests incorporation of the internalolefin (cyclohexene) and free α-olefin(4-vinyl).

Example 241

The catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂C(O)OCH₃ }SbF₆ ⁻(1.703 g, 2 mmol) was added to a 1 gal Hastalloy® autoclave. Theautoclave was sealed, flushed with nitrogen and then charged with 1500 gof SO₂. An over pressure of 3.5 MPa of ethylene was maintained for 24 hrat 25° C. The autoclave was vented to relieve the pressure and thecontents of the autoclave were transferred to a jar. The polymer wastaken up in methylene chloride and purified by precipitation into excessacetone. The precipitated polymer was dried in vacuo to give 2.77 g ofpolymer. The polymer displayed strongbands attributable to sulfonylgroup in the infrared (film on KBr plate) at1160 and 1330 cm⁻¹.

Example 242 Copolymerization of Ethylene and Methyl Vinyl Ketone

Methyl vinyl ketone (MVK) was stirred over anhydrous K₂ CO₃ and vacuumtransferred using a high vacuum line to a dry flask containingphenothiazine (50 ppm). Ethylene and MVK (5 ml) were copolymerized usingthe procedure of Example 125 using as catalyst { (2,6-i-PrPh)₂ DABMe₂!PdCH₂ CH₂ CH₂ C(O)OCH₃)SbF₆ ⁻ (0.084 g, 0.10 mmol) to give 0.46 g ofcopolymer (0.38 g after correcting for catalyst residue). ¹ H NMR(CDCl₃): 0.75-0.95 (m, CH₃);0.95-1.45 (m, CH and CH₂); 1.55 (m, --CH₂CH₂ C(O)CH₃);2.15 (s, --CH₂ CH₂ C(O)CH₃); 2.4 (t, --CH₂ CH₂ C(O)CH₃).Based on the triplet at 2.15, it appeared that much of the ketonefunctionality was located on the ends of the hydrocarbon branches.Integration showed that the copolymer contained 2.1 mole % MVK, and has94methyl carbon (exclusive of methyl ketones) per 1000 methyl carbonatoms. The turnover was 128 equivalents of ethylene and 3 equivalents ofMVK per Pd. GPC (THF, PMMA standard): Mn=5360, Mw=7470, Mw/Mn=1.39.

Example 243

1-Hexene (20 ml) was polymerized in methylene chloride (10 ml) accordingtoexample 173 to give 4.22 g of viscous gel (1002 equivalents 1-hexeneper Pd). Integration of the ¹ H NMR spectrum showed 95 methyl carbonsper1000 methylene carbons. ¹³ C NMR quantitative analysis, branching per1000 CH2: Total methyls (103), Methyl (74.9), Ethyl(none detected),Propyl(none detected), Butyl (12.4), Amyl (none detected), ≧Hexyl andend of chains (18.1). Integration of the CH₂ peaks due to the structure--CH(R)CH₂ CH(R')--, where R is an alkyl group, and R' is an alkyl groupwith two or more carbons showed that in 74% of these structures, R═Me.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR data    TCB, 140 C., 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    42.6359  4.05957       αα for Me & Et.sup.+  branches    37.8987  9.10141       MB.sub.3.sup.+    37.2833  64.4719       αB.sub.1    36.8537  8.67514    35.5381  4.48108    34.8803  4.30359    34.5514  5.20522    34.2755  21.6482    33.2411  4.13499       MB.sub.1    32.9811  32.0944       MB.sub.1    31.9467  14.0714       3B.sub.6.sup.+, 3EOC    30.7212  5.48503       γ + γ + B, 3B.sub.4    30.2597  28.5961       γ + γ + B, 3B.sub.4    30.143   50.4726       γ + γ + B, 3B.sub.4    29.7717  248           γ + γ + B, 3B.sub.4    29.342   17.4732       γ + γ + B, 3B.sub.4    27.5702  27.2867       βγ for 2 Me branches    27.1935  49.5612       βγ + B, (4B.sub.5, etc.)    27.045   23.1776    23.0292  9.56673       2B.sub.4    22.6526  14.1631       2B.sub.5.sup.+, 2EOC    20.2495  5.72164       1B.sub.1    19.7455  48.8451       1B.sub.1    13.9049  21.5008       1B.sub.4.sup.+, 1EOC    ______________________________________

Example 244

1-Heptene (20 ml) was polymerized in methylene chloride (10 ml)according to example 173 to give 1.29 g of viscous gel (263 equivalents1-heptene per Pd). Integration of the ¹ H NMR spectrum showed 82 methylcarbonsper 1000 methylene carbons. ¹³ C NMR quantitative analysis,branching per 1000 CH2: Total methyls (85), Methyl (58.5), Ethyl(nonedetected), Propyl (none detected), Butyl (none detected), Amyl (14.1),≧Hexyl and end of chains (11.1). Integration of the CH₂ peaks due to thestructure --CH(R)CH₂ CH(R')--, where R is an alkyl group, and R' is analkyl group with two or more carbons showed that in 71% of thesestructures, R═Me. DSC (two heats, -150°→150° C., 15° C./min) showsTg=-42° C. and a Tm=28° C. (45 J/g).

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR data    TCB, 120 C., 0.05M CrAcAc    Freq ppm  Intensity    ______________________________________    42.6041   5.16375         αα for Me & Et.sup.+    37.851    15.9779         MB.sub.3.sup.+    37.5963   7.67322    37.2356   99.6734         αB1    35.4956   7.58713    34.8219   6.32649    34.6097   6.37695    34.2278   37.6181    33.3418   3.78275         MB.sub.1    32.9228   60.7999         MB.sub.1    32.2809   13.6249    31.9148   21.2367         3B6.sup.+, 3EOC    30.5886   13.8482         γ + γ + B, 3B.sub.4    30.4613   22.1996         γ + γ + B, 3B.sub.4    30.2173   48.8725         γ + γ + B, 3B.sub.4    30.1059   80.2189         γ + γ + B, 3B.sub.4    29.7292   496             γ + γ + B, 3B.sub.4    29.3049   26.4277         γ + γ + B, 3B.sub.4    27.1511   114.228         βγ + B.sub.1 (4B.sub.5, etc.)    27.0025   47.5199    26.7267   20.4817    24.5623   3.32234    22.6207   36.4547         2B.sub.5.sup.+, 2EOC    20.2176   7.99554         1B.sub.1    19.7084   70.3654         1B.sub.1    13.8677   36.1098         1B.sub.4.sup.+, EOC    ______________________________________

Example 245

1-Tetradecene (20 ml) was polymerized in methylene chloride (10 ml)according to example 173 to give 6.11 g of sticky solid (622 equivalents1-tetradecene per Pd). Integration of the ¹ H NMR spectrum showed 64methyl carbons per 1000 methylene carbons. ¹³ C NMR quantitativeanalysis, branching per 1000 CH2: Total methyls (66), Methyl (35.2),Ethyl(5.6), Propyl (1.2), Butyl (none detected), Amyl (2.1),

≧Hexyl and end of chains (22.8). Integration of the CH₂ peaks due to thestructure --CH(R)CH₂ CH(R')--, where R is an alkyl group, and R' is analkyl group with two or more carbons showed that in 91% of thesestructures, R═Me. The region integrated for the structure where both Rand R' are ≧Ethyl was 40.0 ppm to 41.9 ppm to avoid including a methinecarbon interference.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR data    TCB, 120 C., 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    39.2826  6.684         MB.sub.2    37.8012  8.13042       MB.sub.3.sup.+    37.2171  24.8352       αB.sub.1, 3B.sub.3    34.1694  31.5295       αγ + B, (4B.sub.4, 5B.sub.5, etc.)                           MB.sub.1    33.6809  13.0926       αγ + B, (4B.sub.4, 5B.sub.5, etc.)                           MB.sub.1    32.9004  13.0253       MB.sub.1    31.9022  25.0187       3B.sub.6.sup.+, 3EOC    30.1978  42.5593       γ + γ + B, 3B.sub.4    30.0969  34.1982       γ + γ + B, 3B.sub.4    29.7252  248           γ + γ + B, 3B.sub.4    29.3004  26.4627       γ + γ + B, 3B.sub.4    27.1394  31.8895       βγ + B, 2B.sub.2, (4B.sub.5, etc.)    26.9748  40.5922       βγ + B, 2B.sub.2, (4B.sub.5, etc.)    26.3642  7.06865       βγ + B, 2B.sub.2, (4B.sub.5, etc.)    22.6209  25.5043       2B.sub.5.sup.+, 2EOC    19.6952  15.0868       1B.sub.1    13.8759  24.9075       1B.sub.4.sup.+, 1EOC    10.929   7.63831       1B.sub.2    ______________________________________

Example 246

This example demonstrates copolymerization of ethylene and 1-octene togivepolymer with mostly C6+ branches. Under nitrogen, (2,6-i-PrPh)₂DABH₂ !NiBr₂ (0.005 g, 0.0084 mmol) and 9.6 wt. % MAO in toluene(0.50mL) were dissolved in 10 mL of toluene at room temperature. Theresulting solution was immediately transferred to a 100 mL autoclavethat had previously been flushed with nitrogen and evacuated. 1-Octene(40 mL, 255 mmol) was then added to the reactor, which was subsequentlycharged with ethylene (320 kPa). The reaction mixture was stirred for 60min, during which time the temperature inside the reactor varied between24° and 28° C. Ethylene was then vented, and the product polymer wasprecipitated by addition of the crude reaction mixture to 50 mL ofmethanol containing 5 mL of concentrated aqueous HCl. The polymerprecipitated as a slightly viscous oil; this was removed by pipette anddried affording 3.03 g of amorphous ethylene/1-octene copolymer.Branchingper 1000 CH₂ was quantified by ¹³ C NMR (C₆ D₃ Cl₃, 25° C.):total Methyls (83.6), Methyl (4), Ethyl(1.6), Propyl (4.4), Butyl (5.6),Amyl (10.1), ≧Hex and end of chains (65.8), ≧Am and end of chains(69.3), ≧Bu and end of chains (73.7). GPC (trichlorobenzene vs. linearpolyethylene): M_(w) =48,200, M_(n) =17,000. DSC: Tg=-63° C.

Example 247

This example demonstrates copolymerization of ethylene and 1-octene togivepolymer with mostly methyl and C6+ branches. Under nitrogen,(2,6-i-PrPh)₂ DABH₂ !NiBr₂ (0.005 g, 0.0084 mmol) and 9.6 wt. % MAO intoluene (0.50 mL) were dissolved in 40 mL of toluene at -40° C. Theresulting solution was immediately transferred to a 100mL autoclave thathad previously been flushed with nitrogen and evacuated. 1-Octene (10mL, 64 mmol) was then added to the reactor under 324 kPa of ethylene.The resulting reaction mixture was stirred under 324 kPa of ethylene for1 h 10 min. During this time the temperature inside the reactor variedbetween 29° and 40° C. Ethylene was then vented, and the product polymerwas precipitated by addition of the crude reaction mixture to methanol.The polymer was dried affording 6.45 g of ethylene/1-octene copolymer.Branching per 1000 CH₂ was quantified by ¹³ C NMR (C₆ D₃ Cl₃, 25° C.):Total methyls (50.7), Methyl (13.7), Ethyl(2.4), Propyl (3.5), Butyl(4.1), Amyl (1), ≧Hex and end of chains (26), ≧Am and end of chains(30.4), ≧Bu and end of chains (31). GPC (trichlorobenzene vs. linearpolyethylene): M_(w) =116,000, M_(n) =9,570.

Example 248

Under a nitrogen atmosphere, Ni(COD)₂ (0.017 g, 0.06 mmol) and(2,6-i-PrPh)₂ DABMe₂ (0.024 g, 0.06 mmol) were dissolved in benzene (5.0mL). To the resulting solution was added HBAF (Et₂ O)₂ (0.060 g, 0.06mmol). The resulting solution was immediately frozen inside a 40 mLshaker tube glass insert. The glass insert was transferred to a shakertube, and its contents allowed to thaw under an ethylene atmosphere. Thereaction mixture was agitated under 6.9 MPa C₂ H₄ for 17.5 h at ambienttemperature. The final reaction mixture contained polyethylene, whichwas washed with methanol and dried; yield of polymer=9.2 g. ¹ H NMR(CDCl₂ CDCl₂, 120° C.) showed that this sample contained 49 methyl-endedbranches per 1000 methylenes. DSC: Tm=118.8° C., ΔH_(f) =87.0 J/g.

Example 249

Under a nitrogen atmosphere, Ni P(O-2-C₆ H₄ -Me)₃ !₂ (C₂ H₄) (0.047 g,0.06 mmol) and (2,6-i-PrPh)₂ DABMe₂ (0.024 g, 0.06 mmol) were dissolvedin benzene (5.0 mL). To the resulting solution was added HBAF (Et₂ O)₂(0.060 g, 0.06 mmol). The resulting solution was immediately frozeninside a 40 mL shaker tube glassinsert. The glass insert was transferredto a shaker tube, and its contentsallowed to thaw under an ethyleneatmosphere. The reaction mixture was agitated under 6.9 MPa C₂ H₄ for 18h at ambient temperature. The final reaction mixture containedpolyethylene, which was washed with methanol and dried; yield ofpolymer=8.9 g. ¹ H NMR (CDCl₂ CDCl₂, 120° C.) showed that this samplecontained 47 methyl-ended branches per 1000 methylenes. DSC: Tm=112.1°C., ΔH_(f) =57.5 J/g.

Example 250

A 100 mL autoclave was charged with a solution of Pd₂ (dba)₃(dba=dibenzylideneacetone) (0.054 g, 0.059 mmol) in 40 mL of chloroform.Asolution of (2,6-i-PrPh)₂ DABMe₂ ¥HBAF (Et₂ O)₂ (0.085 g, 0.059 mmol)(see Example 256) in 10 mL of chloroform was then added under 2.1 MPa ofethylene. The reaction mixture was stirred for 3 h.During this time thetemperature inside the reactor varied between 24° and 40° C. Ethylenewas then vented, and the product polymer was precipitated by addition ofthe crude reaction mixture to methanol. The polymer was dried affording14.7 g of viscous polyethylene. ¹ H NMR (CDCl₃, 25° C.) of this materialshowed it to be branched polyethylene with 115 methyl-ended branches per1000 methylenes. GPC analysis in trichlorobenzene gave M_(n) =97,300,M_(w) =225,000 vs. linear polyethylene.

Example 251

A 100 mL autoclave was charged with solid Pd(OAc)₂ (OAc=acetate) (0.027g, 0.12 mmol) and (2,6-i-PrPh)₂ DABMe₂ (0.049 g, 0.12 mmol). The reactorwas flushed with nitrogen and evacuated. A solution of 54 wt. % HBF₄¥Et₂ O (0.098 g, 0.60 mmol) in 10 mL of chloroform was then added under2.1 MPa of ethylene. The reaction mixture was stirred for 1.5 h. Duringthis time, the temperature inside the reactor varied between 24° and 37°C. Ethylene was then vented, and the product polymer was precipitated byaddition of the crude reaction mixture to methanol. The polymer wasdried affording 4.00 g of viscous polyethylene. ¹ H NMR (CDCl₃, 25° C.)of this material showed it to be branched polyethylene with 100methyl-ended branches per 1000 methylenes. GPC analysis intrichlorobenzene gave M_(n) =30,500, M_(w) =43,300 vs. linearpolyethylene.

Example 252

(Note: It is believed that in the following experiment, adventitiousoxygenwas present and acted as a cocatalyst.) Under nitrogen,(2.6-i-PrPh)₂DAB An!Ni(COD) (0.006 g, 0.009 mmol) and 9.6 wt. % MAO intoluene (0.54 mL,1.66 mmol) were dissolved in 50 mL of toluene. Thismixture was then transferred to a 100 mL autoclave. The autoclave wasthen charged with 2.1MPa of ethylene. The reaction mixture was stirredfor 8 min. During this time, the temperature inside the reactor variedbetween 23° and 51° C. Ethylene pressure was then vented. The productpolymer was washed with methanol and dried, affording 8.44 g ofpolyethylene. ¹ HNMR (CDCl₂, 120° C.) showed that this sample contained77 methyl-ended branches per 1000 methylenes.

Example 253

Under nitrogen, (2,4,6-MePh)DABAn!NiBr₂ (0.041 g, 0.065 mmol) wassuspended in cyclopentene (43.95 g, 645 mmol). To this was added a 1Msolution of EtAlCl₂ in toluene (3.2 mL, 3.2 mmol). The resultingreaction mixture was transferred to an autoclave, and under 700 kPa ofnitrogen heated to 60° C. The reaction mixture was stirred at 60° C. for18 h; heating was then discontinued. When the reactor temperature haddropped to ˜30° C., the reaction was quenchedby addition of isopropanol.The resulting mixture was stirred under nitrogen for several minutes.The mixture was then added under air to a 5%aqueous HCl solution (200mL). The precipitated product was filtered off, washed with acetone, anddried to afford 6.2 g of polycyclopentene as a white powder. DSC of thismaterial showed a broad melting transition centered at approximately190° C. and ending at approximately 250° C.; ΔH_(f) =18 J/g. Thermalgravimetric analysis of this sample showed a weight loss starting at184° C.: the sample lost 25% of its weight between 184° and 470° C., andthe remaining material decomposed between 470° and 500° C.

Example 254

Under nitrogen, (2,6-Me-4-BrPh)₂ DABMe₂ !NiBr₂ (0.010 g, 0.015 mmol) wassuspended in cyclopentene (5.0 g, 73.4 mmol). To this was added a 1Msolution of EtAlCl₂ in toluene (0.75 mL, 0.75 mmol). The resultingreaction mixture was stirred at room temperature for 92 h, during whichtime polycyclopentene precipitated. The reaction was then quenched byaddition of ˜5 mL of methanol under nitrogen. Several drops ofconcentrated HCl was then added under air. The product was then filteredoff, washed with more methanol followed by acetone, and dried to afford1.31 g of polycyclopentene as a white powder. DSC of this materialshowed a broad melting transition centered at approximately 200° C.andending at approximately 250° C.; ΔH_(f) =49 J/g. Thermalgravimetricanalysis of this sample showed a weight loss starting at ˜477° C.; thesample completely decomposed between 477° and 507° C.

Example 255

Under nitrogen, (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ (0.008 g, 0.015mmol) wassuspended in cyclopentene (5.00 g, 73.4 mmol). To this was added a 1Msolution of EtAlCl₂ in toluene (0.75 mL, 0.75 mmol). A magnetic stirbarwas added to the reaction mixture and it was stirred at roomtemperature; after 92 h at room temperature the reaction mixture couldno longer be stirred due to precipitation of polycyclopentene solids. Atthispoint the reaction was then quenched by addition of ˜5 mL ofmethanolunder nitrogen. Several drops of concentrated HCl was then addedunder air.The product was then filtered off, washed with more methanolfollowed by acetone, and dried to afford 2.75 g of polycyclopentene as awhite powder.DSC of this material showed a broad melting transitioncentered at approximately 190° C. and ending at approximately 250° C.;ΔH_(f) =34 J/g. Thermal gravimetric analysis of this sample showedaweight loss starting at ˜480° C.; the sample completely decomposedbetween 480° and 508° C.

Example 256

HBAF (0.776 mmol) was dissolved in 5 ml of Et₂ O. A second solutionof0.776 mmol of (2,6-i-PrPh)₂ DABMe₂ in 3 ml of Et₂ O was added. Thereaction turned deep red-brown immediately. After stirring for 2 h thevolatiles were removed in vacuo to give the protonated α-diimine saltwhich was a red crystalline solid.

Example 257

HBF₄ (0.5 mmol) was dissolved in 4 ml of Et₂ O. A second solutionof 0.5mmol of (2,6-i-PrPh)₂ DABMe₂ in 3 ml of Et₂ O was added. A color changeto deep red occurred upon mixing. The reaction was stirred overnight.The volatiles were removed in vacuo to give to give theprotonatedα-diimine salt which was an orange solid.

Example 258

HO₃ SCF₃ (0.5 mmol) was dissolved in 4 ml of Et₂ O. A secondsolution of0.5 mmol of (2,6-i-PrPh)₂ DABMe₂ in 3 ml of Et₂ O was added. A colorchange to deep red occurred upon mixing after a few minutes anyellow-orange precipitate began to form. The reaction was stirredovernight. The product, believed to be the protonated α-diimine salt,was isolated by filtration rinsed with Et₂ O and dried in vacuo.

Example 259

HBAF (0.478 mmol) was dissolved in 5 ml of Et₂ O. A second solutionof0.776 mmol of (2,6-i-PrPh)N═C(CH₃)!₂ CH₂ in 3 ml of Et₂ O was added.The reaction was stirred overnight. Removal of the volatiles in vacuogave an off white solid, believed to be the protonated 1,3-diimine salt.

Example 260

HBF₄ (0.478 mmol) was dissolved in 5 ml of Et₂ O. A second solution of0.478 mmol of (2,6-i-PrPh)N═C(CH₃)!₂ CH₂ in 3 ml of Et₂ O was added, thereaction turned cloudy with a white precipitate. The reaction wasstirred overnight. The white solid, believedto be the protonated1,3-diimine salt, was isolated by filtration rinsed with Et₂ O and driedin vacuo.

Example 261

The product of Example 256 (78 mg) was dissolved in 20 ml of toluene.The reaction vessel was charged with 140 kPa (absolute) of ethylene. Asolution of 10 mg Ni(COD)₂ in 3 ml of toluene was added. Ethylenewasadded (138 kPa pressure, absolute) and the polymerization was run for24 h at ambient temperature. Precipitation with MeOH gave 157 mg ofwhite spongy polyethylene.

Example 262

The product of Example 257 (27 mg) was dissolved in 20 ml of toluene.The reaction vessel was charged with 35 kPa of ethylene. A solution of10 mg Ni(COD)₂ in 3 ml of toluene was added. Ethylene was added (138 kPapressure, absolute) and the polymerization was run for 24 h at ambienttemperature. Precipitation with MeOH gave 378 mg of sticky whitepolyethylene.

Example 263

The product of Example 258 (30 mg) was dissolved in 20 ml of toluene.The reaction vessel was charged with 140 kPa (absolute) of ethylene. Asolution of 10 mg Ni(COD)₂ in 3 ml of toluene was added. Ethylenewasadded (138 kPa pressure, absolute) and the polymerization was run for24 h at ambient temperature. Precipitation with MeOH gave 950 mg ofamorphous polyethylene.

Example 264

To a burgundy slurry of 1 mmol of VCl₃ (THF)₃ in 10 ml of THF wasadded ayellow solution of 1 mmol of (2,6-i-PrPh)₂ DABMe₂ in 4 mlof THF. After10 minutes of stirring the reaction was a homogenous red solution. Thesolution was filtered to remove a few solids, concentrated and thencooled to -30° C. The red crystals that formed were isolated byfiltration, rinsed with pentane and dried in vacuo. The yield was 185mg.

Example 265

The product of Example 264 (6 mg) was dissolved in 20 ml of toluene. Theresulting solution was placed under 140 kPa (absolute) of ethylene. PMAOsolution (0.8 mL, 9.6 wt % Al in toluene) was added and thepolymerizationwas stirred for 3 h. The reaction was halted by theaddition of 10% HCl/MeOH. The precipitated polymer was isolated byfiltration, washed withMeOH and dried in vacuo. The yield was 1.58 g ofwhite polyethylene.

Example 266

Lanthanide metal tris-triflates (wherein the lanthanide metals were Y,La, Sm, Er, and Yb), 1 mmol, was slurried in 10 ml of CH₂ Cl₂. Asolution of 1 mmol of (2,6-i-PrPh)₂ DABMe₂ in 3 ml of CH₂ Cl₂ was addedand the reaction stirred for 16 h at ambient temperature. The solutionwas filtered to give a clear filtrate. Removal of the solvent in vacuogave light yellow to orange powders.

Example 267

Each of the various materials (0.02 mmol) prepared in Example 266 weredissolved in 20 ml of toluene. The resulting solutions were placed under140 kPa (absolute) of ethylene. MMAO-3A solution (1.0 mL, 6.4 wt % Al intoluene) was added and the polymerizations were stirred for 3 h. Thereactions were halted by the addition of 10% HCl/MeOH. The precipitatedpolymers were isolated by filtration washed with MeOH and dried invacuo. Polymer yields are shown the following table,

    ______________________________________    Lanthanide Metal                    Yield (g)    ______________________________________    Yb              0.117    La              0.139    Sm              0.137    Y               0.139    Er              0.167    ______________________________________

Example 268

(2,6-i-PrPh)₂ DABMe₂ !Ni--O₂ (68 mg) was dissolved in 20 mlof toluene.The reaction vessel was placed under 138 kPa (absolute) of ethylene.PMAO (0.7 mL, 9.6 wt. % Al in toluene) was added and the polymerizationwas conducted for 16 h. The reaction was halted by the addition of 15 mlof 10% HCl/MeOH solution. The precipitated polymer was isolated byfiltration and dried under vacuum to yield 1.67 g of rubberypolyethylene.

Example 269

(2,6-i-PrPh)₂ DAEMe₂ !Ni--O₂ (65 mg) was dissolved in 20 mlof toluene.The reaction vessel was placed under 138 kPa (absolute) of ethylene.PMAO (0.7 mL, 9.6 wt. % Al in toluene) was added and the polymerizationwas conducted for 16 h. The reaction was halted by the addition of 15 mlof 10% HCl/MeOH solution. The precipitated polymer was isolated byfiltration and dried under vacuum to yield 1.9 g of rubberypolyethylene.

Example 270

(2,6-i-PrPh)₂ DABMe₂ !CrCl₂ (THF) (15 mg) was dissolved in 20 ml oftoluene. The reaction vessel was placed under 138 kPa (absolute) ofethylene. MMAO-3A (1 mL, 6.4 wt. % Al in toluene) was added and thepolymerization was conducted for 3 h. The reaction was halted by theaddition of 15 ml of 10% HCl/MeOH solution. The precipitated polymer wasisolated by filtration and dried under vacuum to yield 694 mg ofpolyethylene. DSC (-150° to 250° C. at 10° C./min) results from thesecond heating were T_(m) 129° C., ΔH_(f) 204 J/g.

Example 271

(2,6-i-PrPh)₂ DABMe₂ !CrCl₃ (14 mg) was dissolved in 20 ml of toluene.The reaction vessel was placed under 138 kPa (absolute) of ethylene.MMAO-3A (1 mL, 6.4 wt. % Al in toluene) was added and the polymerizationwas conducted for 3 h. The reaction was halted by the addition of 15 mlof 10% HCl/MeOH solution. The precipitated polymer was isolated byfiltration and dried under vacuum to yield 833 mg of polyethylene. DSC(-150° to 250° C. at 10° C./min) results from the second heating wereT_(m) 133° C., ΔH_(f) 211 J/g.

Example 272

(2,6-i-PrPh)₂ DABMe₂ !CrCl₂ (THF) (14 mg) was dissolved in 20 ml oftoluene. The reaction vessel was placed under 138 kPa (absolute) ofethylene. MMAO-3A (1 mL, 6.4 wt. % Al in toluene) was added and thepolymerization was conducted for 3 h. The reaction was halted by theaddition of 15 ml of 10% HCl/MeOH solution. The precipitated polymer wasisolated by filtration and dried under vacuum to yield 316 mg ofpolyethylene. DSC results from the second heating were (-150° to 250° C.at 10° C./min) T_(m) 133° C., ΔH_(f) 107 J/g.

Example 273

(2,6-i-PrPh)₂ DABMe₂ !CrCl₃ (15 mg) was dissolved in 20 ml of toluene.The reaction vessel was placed under 138 kPa (absolute) of ethylene.MMAO-3A (1 mL, 6.4 wt. % Al in toluene) was added and the polymerizationwas conducted for 3 h. The reaction was halted by the addition of 15 mlof 10% HCl/MeOH solution. The precipitated polymer was isolated byfiltration and dried under vacuum to yield 605 mg of polyethylene. DSC(-150° to 250° C. at 10° C./min) results from the second heating wereT_(m) 134° C., ΔH_(f) 157 J/g.

Example 274

A 61 mg sample of { (2,6-i-PrPh)₂ DABAn!Ni(η³ -H₂ CCHCHCl)!BAF wasdissolved in 20 ml of toluene. The reaction vessel was placed under 138kPa (absolute) of ethylene. PMAO (0.7 mL) was added and the reactionstirred for 16 h. The polymerization was quenched by the addition of 15ml of 10% HCl/MeOH. The polymer was isolated by filtration,washed withacetone and dried. The yield was 2.24 g of rubbery polyethylene.

Example 275

A 65 mg sample of { (2,4,6-MePh)₂ DABAn!Ni(η³ -H₂ CCHCHCl)!BAF wasdissolved in 20 ml of toluene. The reaction vessel was placed under 138kPa (absolute) of ethylene. PMAO (0.7 mL) was added and the reactionstirred for 16 h. The polymerization was quenched by the addition of 15ml of 10% HCl/MeOH. The polymer was isolated by filtration,washed withacetone and dried. The yield was 2.0 g of rubbery polyethylene.

Example 276

A 61 mg sample of { (2,6-iPrPh)₂ DABAn!Ni(η³ -H₂ CCHCH₂)}Cl wasdissolved in 20 ml of toluene. The reaction vessel wasplaced under 138kPa (absolute) of ethylene. PMAO (0.7 mL) was added and the reactionstirred for 16 h. The polymerization was quenched by the addition of 15ml of 10% HCl/MeOH. The polymer was isolated by filtration,washed withacetone and dried. The yield was 1.83 g of rubbery polyethylene.

Example 277

A 60 mg sample of { (2,6-iPrPh)₂ DABMe₂ !Ni(η³ -H₂ CCHCH₂)}Cl wasdissolved in 20 ml of toluene. The reaction vessel wasplaced under 138kPa (absolute) of ethylene. PMAO (0.7 mL) was added and the reactionstirred for 16 h. The polymerization was quenched by the addition of 15ml of 10% HCl/MeOH. The polymer was isolated by filtration,washed withacetone and dried. The yield was 1.14 g of rubbery polyethylene.

Example 278 ##STR87## (2,6-i-PrPh)₂ DAB(4-F--Ph)₂ !NiBr₂

In a 250-mL RB flask fitted with pressure equalizing addition funnel,thermometer, magnetic stirrer, and N₂ inlet was placed 0.75 g (3.0 mmol)of 4,4'-difluorobenzil, 13.8 mL (80 mmol) of 2,6-diisopropylaniline(DIPA), and 100 mL dry benzene. In the addition funnel was placed 50 mLofdry benzene and 2.0 mL (3.5 g; 18 mmol) of titanium tetrachloride. Thereaction flask was cooled to 2° C. with ice and the TiCl₄ solution wasadded dropwise over 45 min, keeping the reaction temperature below 5° C.The ice bath was removed after addition was complete and the mixture wasstirred at RT for 72 h. The reaction mixture was partitioned betweenwater and ethyl ether, and the ether phase was rotovapped and theconcentrated oil was washed with 800 mL 1N HCl to remove the excessdiisopropylaniline. The mixture was extracted with 100 mL of ether, andthe ether layer was washed with water and rotovapped. Addition of 15 mLhexane plus 30 mL of methanol to the concentrate resulted in theformation of fine yellow crystals which were filtered, methanol-washed,and dried under suction to yield 0.4 g of (2,6-i-PrPh)₂ DAB(4-F--Ph)₂,mp: 155°-158° C.

A 60-mg (0.092-mmol) sample of (2,6-i-PrPh)₂ DAB(4-F--Ph)₂ was stirredunder nitrogen with 32 mg (0.103 mmol) of nickel (II)dibromide-dimethoxyethane complex in 20 mL of methylene chloride for 66h.The orange-brown solution was rotovapped and held under high vacuumfor 2 hto yield 86 mg of red-brown solids. The solid product was scrapedfrom the sides of the flask, stirred with 20 mL hexane, and allowed tosettle. The yellow-orange hexane solution was pipetted off and theremaining solid washeld under high vacuum to yield 48 mg of theorange-brown complex (2,6-i-PrPh)₂ DAB(4-F--Ph)₂ !NiBr₂.

Example 279 Ethylene polymerization with (2,6-i-PrPh)₂ DAB(4-F--Ph)₂!NiBr₂

A 26-mg (0.033-mmol) sample of (2,6-i-PrPh)₂ DAB(4-F--Ph)₂ !NiBr₂ wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25 mLof dry toluene. Then 0.6 mL of polymethylalumoxane was injected, turningthe orange-brown solution to a deep green-black solution. The mixturewas pressurized immediately with ethylene to 152 kPa(absolute) andstirred at RT for 17 h. The reaction soon became warm to thetouch; thisheat evolution persisted for over an hour and the liquid volumein theSchlenk flask was observed to be slowly increasing. After 17 h, thereaction was still dark green-brown, but thicker and significantly (20%)increased in volume. The ethylene was vented; the off gas-containedabout 3% butenes (1-butene, 1.9%; t-2-butene, 0.6%; c-2-butene, 0.9%) byGC (30-m Quadrex GSQ Megabore column; 50°-250° C. at 10°/min). Thetoluene solution was stirred with 6N HCl/methanol andwas separated; thetoluene was rotovapped and held under high vacuum to yield 9.53 g oflow-melting polyethylene wax. There seemed to be significant low-boilingspecies present, probably low-mw ethylene oligomers, which continued toboil off under high vacuum. ¹ H NMR (CDCl₃ ; 60° C.) of the productshowed a CH₂ :CH₃ ratio of 206:17, which is 57 CH₃ 's per 1000 CH₂ 's.There were vinyl peaks at 5-5.8 ppm; if the end groups are considered tobe vinyls rather than internal olefins, the degree of polymerization wasabout 34.

Example 280 Synthesis of (2-CF₃ Ph)₂ DABMe₂ !NiBr₂ ##STR88## (2-CF₃ Ph)₂DABMe₂ !NiBr₂

A mixture of 10.2 mL (13.1 g; 81.2 mmol) 2-aminobenzotrifluoride and 3.6mL(3.5 g; 41 mmol) freshly-distilled 2,3-butanedione in 15 mL methanolcontaining 6 drops of 98% formic acid was stirred at 35° C. undernitrogen for 8 days. The reaction mixture was rotovapped and theresultantcrystalline solids (1.3 g) were washed with carbontetrachloride. The crystals were dissolved in chloroform; the solutionwas passed through a short alumina column and evaporated to yield 1.0 gof yellow crystals of the diimine (2-CF₃ Ph)₂ DABMe₂. ¹ H NMR analysis(CDCl₃): 2.12 ppm (s, 6H, CH3); 6.77 (d, 2H, ArH, J=9 Hz); 7.20 (t, 2H,ArH, J=7 Hz); 7.53(t, 2H, ArH, J=7 Hz); 7.68 (t, 2H, ArH, J=8 Hz).Infrared spectrum: 1706, 1651, 1603, 1579, 1319, 1110 cm⁻¹. Mp:154°-156° C.

A mixture of 0.207 g (0.56 mmol) of (2-CF₃ Ph)₂ DABMe₂ and 0.202 g (0.65mmol) of nickel(II) dibromide-dimethoxyethane complex in 13 mL ofmethylene chloride was stirred at RT under nitrogen for 3 hr. Thered-brown suspension was rotovapped and held under high vacuum to yield0.3 g of (2-CF₃ Ph)₂ DABMe₂ !NiBr₂ complex.

Example 281 Ethylene polymerization with (2-CF₃ Ph)₂ DABMe₂ !NiBr₂

A 13-mg (0.022-mmol) sample of (2-CF₃ Ph)₂ DABMe₂ !NiBr₂ was placed in aParr® 600-mL stirred autoclave; 200 mL of dry, deaerated hexane (driedover molecular sieves) was added and the hexane was saturated withethylene by pressurizing to 450 kPa (absolute) ethylene and venting.Then 1.0 mL of modified methylalumoxane (1.7M in heptane; contains about30% isobutyl groups) was injected into the autoclave with stirring, andthe autoclave was stirred for 1 hr under 690 kPa (absolute) ethylene asthe temperature rose from 20° C. to 61° C. over the first 20 min andthen slowly declined to 48°C. by the end of the run. The ethylene wasvented and 3 mL of methanol was injected to stop polymerization; theautoclave contained a white suspension of fine particles ofpolyethylene; the appearance was like latex paint. The polymersuspension was added to methanol, and the polymerwas stirred withMeOH/HCl to remove catalyst. The suspension was filtered and dried in avacuum oven (75° C.) to yield 26.8 g of fine, white powderypolyethylene. Differential scanning calorimetry (15° C./min): Tg -45°C.; mp 117° C. (75 J/g). GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): Mn=2,350; Mw=8,640; Mz=24,400; Mw/Mn=3.67. Asolution of the polymer in chlorobenzene could be cast into a waxy filmwith little strength.

Example 282

Under nitrogen, Ni(COD)₂ (0.017 g, 0.062 mmol) and (2,4,6-MePh)₂ DABAn(0.026 g, 0.062 mmol) were dissolved in 2.00 g of cyclopentene to give apurple solution. The solution was then exposed to air (oxygen) forseveral seconds. The resulting dark red-brown solution was then put backunder nitrogen, and EtAlCl₂ (1M solution in toluene, 3.0 mL, 3.0 mmol)added. A cranberry-red solution formed instantly. The reaction mixturewas stirred at room temperature for 3 days, during which timepolycyclopentene precipitated. The reaction was then quenched by theaddition of methanol followed by several drops of concentrated HCl. Thereaction mixture was filtered, and the product polymer washed withmethanol and dried to afford 0.92 g of polycyclopentene as an off-whitepowder. Thermal gravimetric analysis of this sample showed a weight lossstarting at 141° C.: the sample lost 18% of its weight between 141° and470° C., and the remaining material decomposed between 470° and 496° C.

Example 283

Under a nitrogen atmosphere, Ni(COD)₂ (0.017 g, 0.06 mmol) and theligand shown below (0.025 g, 0.06 mmol) were dissolved in benzene (5.0mL). To the resulting solution was added HBAF (Et₂ O)₂ (0.060 g,0.06mmol). The resulting solution was immediately frozen inside a 40 mLshaker tube glass insert. The glass insert was transferred to a shakertube, and its contents allowed to thaw under an ethylene atmosphere. Thereaction mixture was agitated under 6.9 MPa C₂ H₄ for 18 h at ambienttemperature. The final reaction mixture contained polyethylene, whichwas washed with methanol and dried; yield of polymer=11.0 g. ##STR89##

Example 284

The catalyst { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂C(O)OCH₃ }⁺ SbF₆ ⁻(0.025 g, 0.03 mmol) and CH₂ ═CH(CH₂)₆ C₁₀ F₂₁ (4.74 g, 7.52 mmol) weredissolved in 20 mL CH₂ Cl₂ in a Schlenk flask in a drybox. The flask wasconnected to a Schlenk line and the flask was then briefly evacuated andrefilled with ethylene from the Schlenk line. This was stirred at RTunder 1 atm of ethylene for 72 hr. Solvent was evaporated toalmostdryness. Acetone (70 mL) was added and the mixture was stirredvigorously overnight. The upper layer was decanted. The resulting yellowsolid was washed with 3×15 mL acetone, vacuum dried, and 1.15 g ofproduct was obtained. ¹ H NMR analysis (CD₂ Cl₂): 105 methyls per 1000methylene carbons. Comparison of the integral of the CH₂ R_(f) (2.10ppm) with the integrals of methyls(0.8-1.0 ppm) andmethylenes(1.2-1.4ppm) indicated a comonomer content of 6.9 mol %. The polymer exhibited aglass transition temperature of -55° C. (13 J/g) and a melting point of57° C. by differential scanning calorimetry. Gel permeationchromatography (THF, polystyrene standard): Mw=39,500, Mn=34,400,P/D=1.15.

Example 285

In a 100 mL Schlenk flask, (2,6-i-PrPh)₂ DABAn!NiBr₂ (0.012 g, 0.017mmol) and CH₂ ═CH(CH₂)₆ C₁₀ F₂₁ (4.62 g, 7.33 mmol) were dissolved in 32mL of toluene under stirring. This was pressured with 1 atm ethylene andwas allowed to stir at 0° C. for 15 minutes. MAO (1.7 mL, 8.9 wt % intoluene) was added. This was allowed to vigorously stir at RT for 30min. Sixty mL methanol was then added. Thewhite solid was filtered,followed by 3×30 ml 3:1 methanol/toluene wash, vacuum dried, and 3.24 gof white polymer was obtained. ¹ H NMRanalysis(o-dichlorobenzene-d₄,135° C.): 64 methyls per 1000 methylene carbons.Comparison of the integral of the CH₂ R_(f) (2.37 ppm; with theintegrals of methyls (1.1-1.2 ppm) and methylenes (1.4-1.8 ppm)indicated a comonomer content of 8.7 mol %. Mw=281,157, Mn=68,525,P/D=4.1.

Example 286

In a 100 mL Schlenk flask, (2,6-i-PrPh)₂ DABAn!NiBr₂ (0.012 g, 0.017mmol) and CH₂ ═CH(CH₂)₆ C₁₀ F₂₁ (4.62 g, 7.33 mmol) were dissolved in 32mL of toluene under stirring. This was allowed to stir at 0° C. for 15minutes. MAO (1.7 mL, 8.9 wt % in toluene) was added. This was allowedto stir at 0° C. for 2.5 h andthen RT for 3 h. Methanol (200 mL) wasthen added, followed by 1 mL conc. HCl. The white solid was filtered andwashed with methanol, vacuum dried, and 0.79 g of white solid polymerwas obtained. By differential scanning calorimetry, Tm 85° C.(22 J/g)

Example 287

{ (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺ SbF₆ ⁻ (0.0205 g,0.024 mmol) and CH₂ ═CH(CH₂)₄ (CF₂)₄ O(CF₂)₂ SO₂ F (3.5g, 7.26 mmol)were dissolved in 18 mL CH₂ Cl₂ in a Schlenk flask in a drybox. Theflask was connected to a Schlenk line and the flask was then brieflyevacuated and refilled with ethylene from the Schlenk line. This wasstirred at RT under 1 atm of ethylene for 72 hr. Solvent was evaporatedafter filtration. The viscous oil was dissolved in 10 mL CH₂ Cl₂,followed by addition of 100 mL methanol. The upper layer was decanted.The reverse precipitation was repeated two more time, followed by vacuumdrying to yield 3.68 g of a light yellow viscous oil. ¹ H NMR analysis(CDCl₃): 89 methyls per 1000 methylene carbons.Comparison of theintegral of the CH₂ CF₂ -- (2.02 ppm) with the integrals ofmethyls(0.8-1.0 ppm) and methylenes(1.1-1.4 ppm) indicated a comonomercontent of 8.5 mol %. ¹⁹ F NMR (CDCl₃): 45.27 ppm, --SO₂ F; -82.56 ppm,-83.66 ppm, -112.82 ppm, -115.34 ppm, -124.45 ppm, -125.85 ppm, CF₂peaks. The polymer exhibited a glass transitiontemperature of -57° C. bydifferential scanning calorimetry. Gel permeation chromatography (THF,polystyrene standard): Mw=120,000, Mn=78,900, P/D=1.54. The turnovernumbers for ethylene and the comonomer are 2098 and 195, respectively.

Example 288

In a 100 mL Schlenk flask, (2,6-i-PrPh)₂ DABAn!NiBr₂ (0.017 g, 0.024mmol) and CH₂ ═CH(CH₂)₄ (CF₂)₄ O(CF₂)₂ SO₂ F (5.0 g, 10 mmol) weredissolved in 25 mL of toluene under stirring. MAO (2.3 mL, 8.9 wt % intoluene) was added. This was allowed to stir at RT for 15 hr. Sixty mLmethanol was then added, followed by 1 mL conc. HCl. The upper layer wasdecanted, residue washed with methanol(5×5 mL), vacuum dried, and 1.20 gof a white viscous oil was obtained. ¹⁹ F NMR (Hexafluorobenzene, 80°C.): 45.20 ppm, --SO₂ F; -81.99 ppm, -82.97 ppm, -112.00 ppm, -114.36ppm, -123.60 ppm, -124.88 ppm, CF₂ peaks.

Example 289

In a Schlenk flask, (2,6-i-PrPh)₂ DABAn!NiBr₂ (0.012 g, 0.017 mmol) andCH₂ ═CH(CH₂)₄ (CF₂)₄ O(CF₂)₂ SO₂ F (3.26 g, 6.77 mmol) were dissolved in35 mL of toluene under stirring. This was pressured with 1 atm ethyleneand was allowed to stir at 0° C. for 15 minutes. MAO (1.7 mL, 8.9 wt %in toluene) was added. This was allowed to vigorously stir at RT for 45minutes. Methanol (140 mL) was then added, followed by addition of 1 mLofconc. HCl. The white solid was filtered, followed by methanol wash,vacuum dried to obtain 2.76 g of a white rubbery polymer. ¹ H NMRanalysis (o-dichlorobenzene-d₄, 100° C.) 98 methyls per 1000 methylenecarbons. Comparison of the integral of the --CH₂ CF₂ -- (2.02 ppm) withthe integrals of methyls (0.8-1.0 ppm) and methylenes (1.1-1.4 ppm)indicated a comonomer content of 3.5 mol %. ¹⁹ F NMR((O-dichlorobenzene-d₄): 45.19 ppm, --SO₂ F; -82.70 ppm, -83.72 ppm,-112.96 ppm, -115.09 ppm, -124.37 ppm, -125.83 ppm, CF₂ peaks. Thepolymer exhibited Tm of 97° C. by differential scanning calorimetry.Mw=156,000, Mn=90,000, P/D=1.73.

Example 290

{ (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺ SbF₆ ⁻ (0.030 g, 0.035mmol) and CH₂ ═CH(CH₂)₄ (CF₂)₂ CO₂ Et (3.0 g, 11.7 mmol) were dissolvedin 20 mL CH₂ Cl₂ in a Schlenk flask in a drybox. The flask was connectedto a Schlenk line and the flask was then briefly evacuated and refilledwith ethylene from the Schlenk line. This was stirred at RT under 1 atmof ethylene for 72 h. Solvent was evaporated. The viscous oil wasdissolved in 10 mL acetone, followed by addition of 60mL methanol. Themixture was centrifuged. The upper layer was decanted. Theoil wasdissolved in 10 mL acetone followed by addition of 60 mL methanol. Themixture was centrifuged again. The viscous oil was collected, and vacuumdried to obtain 1.50 g of a light yellow viscous oil. ¹ H NMR analysis(CDCl₃): 67 methyls per 1000 methylene carbons. Comparison of theintegral of the CH₂ CF₂ -- (2.02 ppm) with the integrals of methyls(0.8-1.0 ppm) and methylenes (1.1-1.4 ppm) indicated a comonomer contentof 11 mol %. The polymer exhibited a Tg of -61° C. by DSC. GPC (THF,polystyrene standard): Mw=73,800, Mn=50,500, P/D=1.46.

Example 291

In a Schlenk flask, (2,6-i-PrPh)₂ DABAn!NiBr₂ (0.019 g, 0.026 mmol) andCH₂ ═CH(CH₂)₄ (CF₂)₂ CO₂ Et (3.0 g, 11.7 mmol) were dissolved in 35 mLof toluene. This was placed under 1 atm of ethylene at 0° C. for 15minutes. MAO (2.6 mL, 8.9 wt % in toluene) was added. This was allowedto vigorously stir at 0° C. for 30 minutes. Methanol (120 mL) was thenadded, followed by1 mL conc. HCl. The solid was filtered, washed withmethanol and hexane, and vacuum dried to yield 1.21 g of a white rubberysolid. ¹ H NMR analysis (TCE-d₂, 110° C.): Comparison of the integral ofthe CH₂ CF₂ -- (2.06 ppm) with the integrals of methyls(0.8-1.0 ppm)andmethylenes(1.1-1.4 ppm) indicated a comonomer content of 6.0 mol %.Thepolymer exhibited a Tg of -46° C. and Tm's at 40° C. and 82° C. byDSC.

Example 292

In a Schlenk flask, (2,6-i-PrPh)₂ DABAn!NiBr₂ (0.022 g, 0.030 mmol) andCH₂ ═CH(CH₂)₄ (CF₂)₂ CO₂ Et (3.5 g, 13.7 mmol) were dissolved in 30 mLof toluene. This was placed under nitrogen at 0° C. for 15 minutes. MAO(3.0 mL, 8.9 wt % in-toluene) was added. This was allowed to stir at 0°C. for 2.5 h and then RT for 6 h. Fifty mL methanol was then added,followed by 1 mL conc. HCl. The mixture was washed with 3×60 mL water.The organic layer was isolated and dried by using Na₂ SO₄. Evaporationof toluene and addition of hexane resulted in precipitation of an oil.The oil was washed with hexane another two times, and vacuum dried toyield 0.16 g of a yellow oil. Mw=35,600, Mn=14,400, P/D=2.47.

Example 293

{ (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺ SbF₆ ⁻ (0.0848 g, 0.1mmol) and CH₂ ═CH(CH₂)₄ (CF₂)₂ O(CF₂)₂ SO₂ F (11.5 g, 0.03 mol) weredissolved in 72 mL CH₂ Cl₂ in a Schlenk flask in a drybox. The flask wasconnected to a Schlenk line and the flaskwas then briefly evacuated andrefilled with ethylene from the Schlenk line. This was stirred at RTunder 1 atm of ethylene for 72 hr. The solution was filtered throughCelite and then concentrated to 70 mL. Methanol (400 mL) was added understirring. The upper layer was decanted. The oil was redissolved in 70 mLCH₂ Cl₂ followed by addition of350 mL methanol. The viscous oil wascollected, vacuum dried and 24.1 g of a light yellow viscous oil wasobtained. ¹ H NMR analysis (CDCl₃): 113 methyls per 1000 methylenecarbons. Comparison of the integral of the CH₂ CF₂ -- (2.0 ppm) with theintegrals of methyls(0.8-1.0 ppm) and methylenes(1.1-1.4 ppm) indicateda comonomer content of 2.9 mol %. The polymer exhibited a Tg of -66° C.by DSC.GPC (THF, polystyrene standard): Mw=186,000, Mn=90,500, P/D=2.06.The turnover numbers for ethylene and the comonomer are 6,122 and 183,respectively.

Examples 294-300

All of these Examples were done under 1 atm ethylene with a MAconcentration of 1.2M and { (diimine)Pdme(Et₂ O)!⁺ SbF₆ ⁻) concentrationof 0.0022M at RT for 72 hr. Results are shown in the Table below.

    ______________________________________    Ex.    No.  Diimine        MA (mol %)* Mn     P/D    ______________________________________    294  (2,6-i-        6           12,300 1.8         PrPh).sub.2 DABMe.sub.2    295  (2,6-EtPh).sub.2 DABMe.sub.2                        16          7,430  1.9    296  (2,4,6-        23          2,840  2.1         MePh).sub.2 DABMe.sub.2    297  (2,4,6-MePh).sub.2 DABAn                        37          1,390  1.4    298  (2,4,6-MePh).sub.2 DABH.sub.2                        46          1,090  3.1    299  (2-i-PrPh).sub.2 DABMe.sub.2                        17          410    **    300  (2-MePh).sub.2 DABMe.sub.2                        29          320    **    ______________________________________    *In the polymer    **Mn characterized by .sup.1 H NMR.

Example 301

{ (2,6-EtPh)₂ DABMe₂ !PdCH₃ (Et₂ O)}⁺ SbF₆ ⁻ (0.0778 g, 0.10 mmol) andmethyl acrylate (4.78 g, 0.056 mol) were dissolved in 40 mL CH₂ Cl₂ in aSchlenk flask in a drybox. The flask was connected to a Schlenk line andthe flask was then briefly evacuated and refilled with ethylene from theSchlenk line. This was stirred at RT under 1 atm of ethylene for 72 h.The mixture was filtered through silica gel, solvent was evaporated andthen vacuum dried,and 1.92 g light of a yellow viscous oil was obtained.¹ H NMR analysis (CDCl₃): 69 methyls per 1000 methylene carbons.Comparison of the integral of the methyl on the ester groups (2.3 ppm)with the integrals of carbon chain methyls(0.8-1.0 ppm) andmethylenes(1.1-1.4 ppm)indicated a comonomer content of 16 mol %. Thepolymer exhibited a Tg of -68° C. by DSC. GPC (THF, polystyrenestandard): Mw=14,300, Mn=7,430, P/D=1.93.

Example 302

{ (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺ SbF₆ ⁻ (0.254 g, 0.30mmol) and CH₂ ═CHCO₂ CH₂ (CF₂)₆ CF₃ (90.2 g, 0.20 mol) weredissolved in150 mL CH₂ Cl₂ in a flask in the drybox. The flask was connected to aSchlenk line and the flask was then briefly evacuated and refilled withethylene from the Schlenk line. This was stirred at RT under 1 atm ofethylene for 24 h. The solution was decanted to 1200 mL methanol,resulted formation of oil at the bottom of the flask. The upper layerwas decanted, oil dissolved in 150 mL CH₂ Cl₂, followed byaddition of1200 mL of methanol. The upper layer was decanted, oil dissolved in 600mL hexane and filtered through Celite®. Solvent was evaporated, and thenvacuum dried, yielding 54.7 g of a viscous oil. ¹ H NMR analysis(CDCl₃): 99 methyls per 1000 methylene carbons.Comparison of theintegral of the CH₂ CF₂ -- (4.56 ppm) with the integrals ofmethyls(0.8-1.0 ppm) and methylenes(1.1-1.4 ppm) indicated a comonomercontent of 5.5 mol %. The polymer exhibited a Tg of -49° C. by DSC.Mw=131,000, Mn=81,800.

Example 303

{ (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺ SbF₆ ⁻ (0.169 g, 0.20mmol) and β-hydroxyethyl acrylate (6.67 g, 0.057 mol) were dissolved in40 mL CH₂ Cl₂ in a flask in the drybox. The flask was connected to aSchlenk line and the flask was then briefly evacuated and refilled withethylene from the Schlenk line. This was stirred at RT under 1 atm ofethylene for 45 h. Solvent was evaporated. The residue was dissolved in100 mL hexane, followed by addition of 400 mL methanol. Upon standingovernight, a second upper layer formed and was decanted. The oil wasdissolved in 60 mL THF, followed by addition of 300 mL water. The upperlayer was decanted. The residue was dissolved in 100 mL 1:1 CH₂ Cl₃/hexane. This was filtered through Celite®. The solvent was evaporated,vacuum dried and 6.13 g of a light yellow oil was obtained. ¹ H NMRanalysis (CD₂ Cl₂): 142 methyls per 1000 methylene carbons. Comparisonof the integral of the CH₂ CO₂ -- (2.30 ppm)with the integrals ofmethyls(0.8-1.0 ppm) and methylenes(1.1-1.4 ppm) indicated a comonomercontent of 2.6 mol %. Mw=53,100, Mn=37,900, P/D=1.40.

Example 304

{ (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺ SbF₆ ⁻ (0.169 g, 0.20mmol) and hydroxypropyl acrylate (7.52 g, 0.058 mol) were dissolved in40 mL CH₂ Cl₂ in a flask in the drybox. The flask was connected to aSchlenk line and the flask was then briefly evacuated and refilled withethylene from the Schlenk line. This was stirred at RT under 1 atm ofethylene for 72 h. Solvent was evaporated. Eighty mL methanol was addedtodissolve the residue, followed by 250 mL water. The upper layer wasdecanted. The reverse precipitation was repeated one more time. The oilwas isolated, vacuum dried, and 1.1 g of a light yellow oil wasobtained. ¹ H NMR analysis (CD₂ Cl₂): 94 methyls per 1000 methylenecarbons. Comparison of the integral of the CH₂ CO₂ -- (2.30 ppm)with theintegrals of methyls(0.8-1.0 ppm) and methylenes(1.1-1.4 ppm) indicateda comonomer content of 6.5 mol %. Mw=39,200, Mn=28,400, P/D=1.38.

Example 305

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed into a glass vial inthe dry box (0.0141 g, 0.025 mmol). Cyclopentene was added (3.41 g,2,000 equivalents/Ni). A solution of MMAO (Akzo Nobel MMAO-3A,modifiedmethylaluminoxane, 25% isobutyl groups in place of methylgroups) was addedwhile stirring (0.75 ml, 1.7M Al in heptane, 50equivalents/Ni). Following addition of the MMAO, the solution washomogeneous. After stirring for several hours, solid polymer started toprecipitate. After stirring for 46hours, the solution was filtered andthe solids were washed several times on the filter with pentane. Thepolymer was dried in vacuo for 12 hours atroom temperature to yield 0.66g polymer (388 turnovers/Ni). The polymer was pressed at 292° C. to givea transparent, light gray, tough film. DSC (25° to 300° C., 15° C./min,second heat): Tg=104° C., Tm (onset)=210° C., Tm (end)=285° C., Heat offusion=14 J/g. X-ray powder diffraction shows peaks at d-spacings 5.12,4.60, 4.20, 3.67, and 2.22. ¹ H NMR (500 MHz, 155° C., d₄-o-dichlorobenzene, referenced to downfield peak of solvent=7.280 ppm):0.923 (bs, 1.0H, --CHCH₂ CH--); 1.332 (bs, 2.0H, --CHCH₂ CH₂ CH--);1.759 (bs, 4.0H, --CHCH₂ CH₂ CH-- and --CHCH₂ CH₂ CH--); 1.947 (bs,1.0H, --CHCH₂ CH--). The assignments are based upon relative integralsand ¹ H-¹³ C correlations determined by 2D NMR. This spectrum isconsistent with an addition polymer with cis-1,3 enchainment of thecyclopentene.

Example 306

Cyclopentene was polymerized by (2,4,6-MePh)₂ DABMe₂ !PdMeCl andMMAOaccording to Example 305 to give 0.37 g polymer (217 turnovers/Pd). Thepolymer was pressed at 250° C. to give a transparent, light brown, toughfilm. DSC (25° to 300° C., 15° C./min, second heat): Tg=84° C.,Tm(onset)=175° C., Tm (end)=255° C., Heat of fusion=14 J/g. ¹ H NMR (400MHz, 120° C., d₄ -o-dichlorobenzene, referenced to downfield peak ofsolvent=7.280 ppm): 0.90 (bs, 1H, --CHCH₂ CH--); 1.32 (bs, 2H, --CHCH₂CH₂ CH--); 1.72, 1.76 (bs, bs 4H, --CHCH₂ CH₂ CH-- and --CHCH₂ CH₂CH--); 1.94 (bs, 1H, --CHCH₂ CH--). The assignments are based uponrelative integrals and ¹ H-¹³ C correlations determined by 2D NMR. Thisspectrum is consistent with an addition polymer with cis-1,3 enchainmentof the cyclopentene.

Example 307

Cyclopentene was polymerized by (2,6-EtPh)₂ DABMe₂ !PdMeCl and MMAOaccording to Example 305 to give 0.39 g polymer (229 turnovers/Pd). Thepolymer was pressed at 250° C. to give a transparent, light brown, toughfilm. DSC (25° to 300° C., 15° C./min, second heat): Tg=88° C.,Tm(onset)=175° C., Tm (end)=255° C., Heat of fusion=16 J/g. ¹ H NMR (300MHz, 120° C., d₄ -o-dichlorobenzene) is very similar to the spectrum ofExample 306.

Example 308

Cyclopentene was polymerized by (2,4,6-MePh)₂ DABMe₂ !NiBr₂and MMAOaccording to Example 305 to give 0.36 g polymer (211 turnovers/Ni). Thepolymer was pressed at 250° C. to give a transparent, colorless, toughfilm. DSC (25° to 300° C., 15° C./min, second heat): Tg=98° C.,Tm(onset)=160° C., Tm (end)=260° C., Heat of fusion=22 J/g. ¹ H NMR (500MHz,120° C., d₄ -o-dichlorobenzene) is very similar to the spectrumofExample 306. X-ray powder diffraction shows the same crystalline phaseas observed in Example 305.

Example 309

Cyclopentene was polymerized by (2,6-i-PrPh)₂ DABMe₂ !PdMeCl andMMAOaccording to Example 305 to give 0.73 9 of fine powder (429turnovers/Pd). The polymer was pressed at 250° C. to give a transparent,light brown tough film. DSC (25° to 300° C., 15° C./min, second heat):Tg=96° C., Tm(onset)=175° C., Tm (end)=250° C., Heat of fusion=14 J/g. ¹H NMR (400 MHz,120° C., d₄ -o-dichlorobenzene) is very similar to thespectrumof Example 306. X-ray powder diffraction shows the samecrystalline phase as observed in Example 305.

Example 310

Cyclopentene was polymerized by (2,6-i-PrPh)₂ DABMe₂ !PdCl₂and MMAOaccording to Example 305 to give 0.856 g polymer (503 turnovers/Pd). Thepolymer was pressed at 250° C. to give a transparent, light brown, toughfilm. DSC (25° to 300° C., 15° C./min, second heat): Tg=104° C.,Tm(onset)=140° C., Tm (end)=245° C., Heat of fusion=19 J/g. ¹ H NMR (400MHz,120° C., d₄ -o-dichlorobenzene) is very similar to the spectrumofExample 306.

Example 311

Cyclopentene was polymerized by (2,6-EtPh)₂ DABMe₂ !NiBr₂ and MMAOaccording to Example 305 to give 0.076 g polymer (45 turnovers/Ni). ¹ HNMR (400 MHz, 120° C., d₄ -o-dichlorobenzene) is very similar to thespectrum of Example 306.

Example 312

Cyclopentene was polymerized by (2,4,6-MePh)₂ DABH₂ !NiBr₂ and MMAOaccording to Example 305 to give 0.66 g polymer (388 turnovers/Ni). Thepolymer was pressed at 292° C. to give a tough film. ¹ H NMR (400 MHz,120° C., d₄ -o-dichlorobenzene) is very similar to the spectrum ofExample 306. A DSC thermal fractionation experiment was done in which asample was heated to 330° C. at 20° C./minute followed by stepwiseisothermal equilibration at the followed temperatures (times): 280° C.(6 hours), 270° C. (6 hours), 260° C. (6 hours), 250° C.(6 hours), 240°C. (4 hours), 230° C. (4 hours), 220° C. (4 hours), 210° C. (4 hours),200° C. (3 hours), 190° C. (3 hours), 180° C. (3 hours), 170° C. (3hours), 160° C. (3 hours), 150° C. (3 hours). The DSC of this sample wasthen recorded from 0° C.-330° C. at 10° C./min. Tg=98° C., Tm(onset)=185° C., Tm (end)=310° C., Heat of fusion=35 J/g.

Example 313

Cyclopentene was polymerized by (2-PhPh)₂ DABMe₂ !NiBr₂ andMMAOaccording to Example 305 to give 1.24 g polymer (728 turnovers/Ni). Thepolymer was pressed at 292° C. to give a transparent, light gray,brittle film. DSC (25° to 320° C., 10° C./min, second heat):Tm(onset)=160° C., Tm (end)=285° C., Heat of fusion=33 J/g. ¹ H NMR (400MHz, 120° C., d₄ -o-dichlorobenzene) is very similar to the spectrum ofExample 306. Several peaks attributed to cyclopentenyl end groups wereobserved in the range 5.2-5.7 ppm. Integration of these peaks was usedto calculate M_(n) =2130. IR (pressed film, cm⁻¹): 3050 (vw, olefinicend group,CH stretch), 1615(vw, olefinic end group, cis-CH═CH-- doublebond stretch), 1463(vs), 1445(vs), 1362(s), 1332(s), 1306(s), 1253(m),1128(w),1041(w), 935(m), 895(w), 882(w), 792(w), 721(w, olefinic endgroup, cis-CH═CH--, CH bend). GPC (Dissolved in 1,2,4-trichlorobenzeneat 150° C., run at 100° C. in tetrachloroethylene, polystyrenecalibration): Peak MW=13,900; M_(n) =10,300; M_(w) =17,600; M_(w) /M_(n)=1.70.

Example 314

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed into a glass vial inthe dry box (0.032 g, 0.050 mmol). Toluene (2.35 ml) and cyclopentene(6.81 g, 2,000 equivalents/Ni) were added, followed by C₆ H₅ NHMe₂ ⁺B(C₆ F₅)₄ ⁻ (0.04 g, 50 equivalents/Ni). A solution of Et₃ Al was addedwhile stirring (2.5 ml, 1M in heptane, 50 equivalents/Ni). Afterstirring for 46 hours, the solution was filtered and the solids werewashed several times on the filter with pentane. The polymer was driedin vacuo for 12 hours at room temperature to yield 0.16 g of fine powder(47 turnovers/Ni). A control experiment with no C₆ H₅ NHMe₂ ⁺ B(C₆ F₅)₄⁻ gave no polymer.

Example 315

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed into a glass vial inthe dry box (0.032 g, 0.050 mmol). Toluene (3.46 ml ) and cyclopentene(6.81 g, 2,000 equivalents/Ni) were added. A solution of Et₂ AlCl wasadded while stirring (1.39 ml, 1.8M in toluene, 50 equivalents/Ni).After stirring for 46 hours, the solution was filtered and the solidswere washed several times on the filter with pentane. The polymer wasdried in vacuo for 12 hours at room temperature to yield 0.53 g of finepowder (156 turnovers/Ni).

Example 316

The complex (2,4,6-MePh)₂ DABMe₂ !NiBr₂ was weighed into a glass vial inthe dry box (0.0070 g, 0.0130 mmol). Pentane (2.2 ml ) and cyclopentene(10.0 g, 11,300 equivalents/Ni) were added. A solution of EtAlCl₂ wasadded while stirring (0.73 ml, 1.0M in hexanes, 56 equivalents/Ni).After stirring for 192 hours, the solution was filtered and the solidswere washed several times on the filter with pentane. The polymer wasdried in vacuo for 12 hours at room temperature to yield 2.66 g of finepowder (3010 turnovers/Ni). The polymer was mixed with 200 ml ofMeOH ina blender at high speed to produce a fine powder. The solid wascollected by filtration and then mixed for 1 hour with 39 ml of a 1:1mixture of MeOH/concentrated aqueous HCl. The solid was collected byfiltration, washed with distilled water, and then washed on the filter3× with 20 ml of a 2 wt. % solution of Irganox® 1010 in acetone.Thepolymer was dried in vacuo for 12 hours at room temperature. DSC (25° to300° C., 10° C./min, controlled cool at 10° C./min, second heat): Tg=98°C., Tm(onset)=160° C., Tm (end)=240° C., Heat of fusion=17 J/g. TGA(air,10° C./min): T(onset of loss)=330° C. T(10% loss)=450° C. ¹³ C NMR (500MHz ¹ H frequency, 3.1 ml of 1,2,4-trichlorobenzene, 0.060 g Cr(acac)₃,120° C.): 30.640 (s, 2 C), 38.364 (s, 1 C), 46.528 (s, 2 C). Thisspectrum is consistent with an addition polymer of cyclopentene withcis-1,3-enchainment. A sample of the polymer was melted in a Schlenktube under a nitrogen atmosphere. Fibers were drawn from the moltenpolymer using a stainless steel cannula with a bent tip. A nitrogenpurge was maintained during the fiber drawing. The fibers were tough andcould be drawn about 2× by pulling against a metal surface heated to125° C.

Example 317

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed into a glass vial inthe dry box (0.0093 g, 0.0146 mmol). Cyclopentene (10.0 g, 10,000equivalents/Ni) was added. A solution of EtAlCl₂ was added whilestirring (0.73 ml, 1.0M in hexanes, 50 equivalents/Ni). After stirringfor168 hours, the solution was filtered and the solids were washedseveral times on the filter with pentane. The polymer was dried in vacuofor 12 hours at room temperature to yield 4.66 g of fine powder (4660turnovers/Ni). The polymer was mixed with 200 ml of MeOH in a blender athigh speed to produce a fine powder. The solid was collected byfiltrationand then mixed for 1 hour with 39 ml of a 1:1 mixture ofMeOH/concentrated aqueous HCl. The solid was collected by filtration,washed with distilled water, and then washed on the filter 3× with 20 mlof a 2 wt. % solution of Irganox 1010 in acetone. The polymer was driedin vacuo for 12hours at room temperature. DSC (25° to 350° C., 15°C./min, second heat): Tg=97° C., Tm(onset)=160° C., Tm (end)=285° C.,Heat of fusion=25 J/g. ¹³ C NMR (500 MHz ¹H frequency, 3.1 ml of1,2,4-trichlorobenzene, 0.060 g Cr(acac)₃, 120° C.): 30.604 (s, 2 C),38.333 (s, 1 C), 46.492 (s, 2 C). This spectrum is consistent with anaddition polymer of cyclopentene with cis-1,3-enchainment. A sample ofthe polymer was melted in a Schlenk tube under a nitrogen atmosphere.Fibers were drawn from the molten polymer using a stainless steelcannula with a bent tip. A nitrogen purge was maintained during thefiber drawing. The fibers were tough and could be drawn about 2× bypulling against a metal surface heated to 125° C. GPC (Dissolved in1,2,4-trichlorobenzene at 150° C.,run at 100° C. in tetrachloroethylene,polystyrene calibration): Peak MW=137,000; M_(n) =73,000; M_(w)=298,000; M_(w) /M_(n) =4.08.

Example 318

The complex { (2,6-i-PrPh)₂ DABMe₂ !PdMe(Et₂ O)}⁺ SbF₆ ⁻ (0.05 g, 0.060mmol) was added to 10.0 g of stirring cyclopentene. Solid polymer formedrapidly and precipitated. The polymer was isolated by filtration, washedon the filter 3× with pentane, and dried in vacuo at room temperature togive 1.148 g finely divided powder (282 turnovers/Pd). DSC (25° to 350°C., 15° C./min, first heat): Tm(onset)=175° C., Tm (end)=245° C., Heatof fusion=16 J/g.

Example 319

The complex { (2,6-i-PrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺ SbF₆ ⁻(0.05 g, 0.059 mmol) was added to 10.0 g of stirring cyclopentene. Thecomplex is not very soluble in cyclopentene. The amount of solidsincreased slowly. After 27 days, the solid polymer was isolated byfiltration, washed on the filter 3× with pentane, and dried in vacuo atroom temperature to give 1.171 g finely divided powder (292turnovers/Pd). DSC (25° to 350° C., 15° C./min, first heat):Tm(onset)=170° C., Tm (end)=255° C., Heat of fusion=24 J/g.

Example 320

The complex (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ was weighed into a glass vial inthe dry box (0.025 g, 0.040 mmol). Cyclopentene (10.0 g, 1,000equivalents/Ni) was added. A solution of MMAO was added while stirring(0.802 ml, 2.5M in heptane, 50 equivalents/Ni). After stirring for 5minutes, the mixture was rusty brown and still contained some solids. Anadditional 50 equivalents of MMAO were added and the solution becamehomogeneous. After 12 hours, the mixture was filtered and the solidswere washed several times on the filter with pentane. The polymer wasdried in vacuo for 12 hours at room temperature to yield 0.238 g of finepowder (87 turnovers/Ni). DSC (25° to 350° C., 15° C./min, second heat):Tm(onset)=170° C., Tm (end)=265° C., Heat of fusion=18 J/g.

Example 321

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed into a glass vial inthe dry box (0.0093 g, 0.0146 mmol). Cyclopentene (10.0 g, 10,000equivalents/Ni) and anhydrous methylene chloride (48.5 ml) were added. Asolution of EtAlCl₂ was added while stirring (2.92 ml, 1.0M in toluene,200 equivalents/Ni). After stirring for 163 hours, the solution wasfiltered and the solids were washed several times on the filter withpentane. The polymer was dried in vacuo for 12 hours at room temperatureto yield 1.64 g of fine powder (1640 turnovers/Ni). A DSC thermalfractionation experiment was done according to the procedure of Example312. A DSC was then recorded from 0° C. to 330° C. at 10° C./min. Tg=92°C., Tm (onset)=150° C., Tm (end)=250° C., Heat of fusion=11.4 J/g.

Example 322

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed into a glass vial inthe dry box (0.0093 g, 0.0146 mmol). Cyclopentene (10.0 g, 10,000equivalents/Ni) was added. A solution of i-BuAlCl₂ was added whilestirring (2.92 ml, 1.0M in toluene, 200 equivalents/Ni). After stirringfor 163 hours, the solution was filtered and the solids were washedseveral times on the filter with pentane. The polymer was dried in vacuofor 12 hours at room temperature to yield 1.99 g of fine powder (1990turnovers/Ni). The polymer was pressed at 292° C. to give a transparent,light gray, tough film. A DSC thermal fractionation experiment was doneaccording to the procedure of Example 312. A DSC was then recorded from0° C. to 330° C. at 10° C./min. Tg=103° C., Tm (onset)=150° C., Tm(end)=290° C., Heat of fusion=27 J/g.

Example 323

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed into a glass vial inthe dry box (0.0932 g, 0.146 mmol). Cyclopentene (5.0 g, 500equivalents/Ni) and toluene (6.54 ml) were added. A solution of PMAO(AkzoNobel Polymethylaluminoxane) was added while stirring (3.16 ml,2.32M Al intoluene, 50 equivalents/Ni). After stirring for 163 hours,the solution wasfiltered and the solids were washed several times on thefilter with pentane. The polymer was dried in vacuo for 12 hours at roomtemperature to yield 3.64 g of fine powder (364 turnovers/Ni). Thepolymer was pressedat 292° C. to give a brown film that seemed tough,but failed along a straight line when it broke. A DSC thermalfractionation experiment was done according to the procedure of Example312 was then recorded from 0° C. to 330° C. at 10° C./min. Tg=100° C.,Tm(onset)=150° C., Tm (end)=270° C., Heat of fusion=21 J/g.

Example 324

A mixture of 20 mg (0.032 mmol) of NiBr₂ (2,6-i-PrPh)₂ DABMe₂ ! wasmagnetically-stirred under nitrogen in a 50-mL Schlenk flask with 15 mLof dry, deaerated toluene as 0.6 mL of 3M poly(methylalumoxane) wasinjected via syringe. The mixture became deep blue-black. Then 2.5 mL(14 mmol) of beta-citronellene, (CH₃)₂ C═CHCH₂ CH₂ CH(CH₃)CH═CH₂, wasinjected and the mixture was immediately pressurized with ethylene at190 kPa (absolute) and was stirred at 23° C. for 17 h; by the end of 17h, the solution was too thick to stir. The ethylene was vented and thetoluene solution was stirred with 6N HCl and methanol and was decanted.The polymer was stirred with refluxing methanol for an hour to extractsolvent; oven-drying yielded 0.90 g of rubbery polyethylene. ¹ H NMR(CDCl₃) showed a CH₂ :CH₃ ratio of 83:12, which is 101 CH₃ 's per 1000CH₂ 's; there were small peaks for the beta-citronellene isopropylidenedimethyls (1.60 and 1.68 ppm), as well asa tiny peak for vinyl H (5.0ppm); diene incorporation was estimated at 0.7mol %. Differentialscanning calorimetry: -51° C. (Tg). GPC data (trichlorobenzene, 135° C.;PE standard): Mn=23,200; Mw=79,200; Mz=154,000; Mw/Mn=3.42.

Example 325

A 15-mg (0.024-mmol) sample of NiBr₂ (2,6-i-PrPh)₂ DABMe₂ !wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25mLof dry, deaerated toluene and 5 mL (27 mmol) of dry, deaerated1,9-decadiene. Then 0.6 mL of polymethylalumoxane (1.7M MAO in heptane;contains about 30% isobutyl groups) was injected; the tan suspension didnot change color. The mixture was pressurized with ethylene to 190 kPa(absolute) and was stirred for 1 hr; it began to grow green-gray anddarker in color, so 0.6 mL more MAO was added, after which the mixturesoon turned deep green-black. The reaction was stirred for 16 hr and theethylene was then vented; by this time the solution had become thick andunstirrable. The mixture was stirred with refluxing 6N HCl and methanol,and the polymer was washed with methanol, pressed free of solvent, anddried under high vacuum to yield 1.0 g of rubbery polyethylene. Thepolymer was insoluble in hot dichlorobenzene, demonstratingincorporation of the diene.

Example 326

A 21-mg (0.034-mmol) sample of NiBr₂ (2,6-i-PrPh)₂ DABMe₂ !wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25mLof dry, deaerated toluene. Then 0.6 mL of 2.9M polymethylalumoxane wasinjected; the red-brown suspension became deep green. The mixture waspurged with ethylene and then 2.0 mL (1.4 g; 15 mmol) of2-methyl-1,5-hexadiene was added; the mixture was pressurized withethylene to 190 kPa and was stirred for 18 h; the solution became brown.The ethylene was vented and the toluene solution was stirred with 6N HCland methanol and was separated; rotary evaporation of the toluene layeryielded, after acetone washing to remove catalyst, 47 mg of viscousliquidpolymer. ¹ H NMR (CDCl₃) showed a CH₂ :CH₃ ratio of 82:15, whichis 130 CH₃ 's per 1000 CH₂ 's. There were also peaks for theincorporated diene at 1.72 ppm (0.5H; CH₃ --C═CH₂) and 4.68 ppm (0.3H;CH₃ --C═CH₂) and no evidence of terminal vinyl (--CH═CH₂ ; 4.95 and 5.80ppm) from unincorporated diene. The level of diene incorporation wasabout 0.7 mol %.

Example 327

A 30-mg (0.049-mmol) sample of NiBr₂ (2,6-i-PrPh)₂ DABMe₂ !wasmagnetically stirred under nitrogen in a 50-mL Schlenk flask with 25mLof dry, deaerated toluene. Then 1.0 mL of methylalumoxane (1.7M inheptane;contains about 30% isobutyl groups) was injected; the red-brownsuspension became deep green. The mixture was saturated with ethyleneand then 0.5 mL(0.38 g; 3.0 mmol) of 2-methyl-2,7-octadiene was added;the mixture was pressurized with ethylene to 190 kPa (absolute) and wasstirred for 18 h; the solution became brown. The ethylene was vented andthe toluene solution was stirred with 6N HCl and methanol and wasseparated; rotary evaporation of the toluene yielded, after acetonewashing to remove catalyst, 0.15 g of viscous liquid polymer. ¹ H NMR(CDCl₃) showed a CH₂ :CH₃ ratio of 81.5:13.5, which is 117 CH₃ 's per1000 CH₂ 's. The level of diene incorporation was about 0.5-1.0 mol %,judging from the diene isopropylidene methyls at 1.60 and 1.69 ppm.

Examples 328-335

Acrylate Chelate Complexes

The chelate complexes for these examples were generated in situ for NMRstudies by the reaction of (ArN═C(R)--C(R)═NAr)PdMe(OEt₂)!BAF with H₂C═CHC(O)OR' and on a preparative scale by the reaction of NABAF with(ArN═C(R)--C(R)═NAr)PdMeCl and H₂ C═CHC(O)OR' (vide infra). In theseexamples, the following labeling scheme is used to identify thedifferent chelate complexes that were observed and/or isolated.Assignments of all ¹ H NMR chelate resonances were confirmed byhomonuclear decoupling experiments. ##STR90##

General Procedure for the Synthesis of Chelate Complexes

A gastight microliter syringe was used to add 1.1 equiv of H₂C═CHC(O)OR' to a mixture of 1 equiv of NaBAF and 1 equiv of(2,6-i-PrPh)₂ DABR₂)PdMeCl suspended in 25 mL of Et₂ O. The sides of theSchlenk flask were rinsed with an additional 25 mL of Et₂ O and thereaction mixture was stirred for 1-2 days at RT. Sodiumchloride wasremoved from the reaction mixture via filtration, yielding a clearorange solution. The Et₂ O was removed in vacuo and the productwaswashed with hexane and dried in vacuo. For R'═Me or t-Bu, no furtherpurification was necessary (yields >87%). Recrystallization lowered theyield of product and did not result in separation of the isomericmixtures.

For R'=--CH₂ (CF₂)₆ CF₃, contamination of the product with unreactedNaBAF was sometimes observed. Filtration of a CH₂ Cl₂ solution of theproduct removed the NaBAF. The CH₂ Cl₂ was then removed in vacuo toyield a partially oily product. A brittle foam was obtained bydissolving the product in Et₂ O and removing theEt₂ O in vacuo(yields >59%). Although isolable, chelate complexes derived from FOAtended to be less stable than those derived from MA or t-BuA anddecomposed with time or additional handling.

Spectral Data for the BAF Counterion

The following ¹ H and ¹³ C spectroscopic assignments of the BAFcounterion in CD₂ Cl₂ were invariant for different complexesandtemperatures and are not repeated in the spectroscopic data for eachof thecationic complexes: (BAF). ¹ H NMR (CD₂ Cl₂) δ7.74 (s,8, H_(o)),7.57 (s, 4, H_(p)); ¹³ C NMR (CD₂ Cl₂) δ162.2 (q, J_(CB) =37.4,C_(ipso)), 135.2 (C_(o)), 129.3 (q, J_(CF) =31.3, C_(m)), 125.0 (q,J_(CF) =272.5, CF₃), 117.9 (C_(p)).

Example 328

The above synthesis using (2,6-i-PrPh)₂ DABH₂ !PdMeCl (937 mg, 1.76mmol), NaBAF (1.56 g, 1.75 mmol), and MA (175 μL, 1.1 equiv) wasfollowed and the reaction mixture was stirred for 12 h. The resultingorange powder (2.44 g, 96.0%) consisted of a mixture of 6a(Me) (91%),5'a(Me) (5%), and 5a(Me) (4%), according to ¹ H NMR spectroscopy.6a(Me): ¹ H NMR (CD₂ Cl₂, 400 MHz, rt) δ8.31 and 8.26(s, 1 each,N═C(H)--C'(H)═N), 7.5-7.2 (m, 6, H_(aryl)), 3.17 (s, 3, OMe), 3.14 and3.11 (septet, 2 each, CHMe₂ and C'HMe₂), 2.48 (t, 2, J=5.8, CH₂ C(O)),1.75 (t, 2, J=5.8, PdCH₂), 1.38, 1.32, 1.25 and 1.22 (d, 6 each, J=6.8,CHMeMe' and C'HMeMe'), 0.73 (pentet, 2, J=5.8, PdCH₂ CH₂ CH₂ C(O)); ¹³ CNMR (CD₂ Cl₂, 100 MHz, rt) δ183.9 (C(O)), 167.1 (J_(CH) =181.4, N═C(H)),160.7 (J_(CH) =181.3, N═C'(H)), 142.9 and 142.4 (Ar, Ar': C_(ipso)),139.7 and 138.7 (Ar, Ar': C_(ipso)), 129.8 and 129.0 (Ar, Ar': C_(p)),124.6 and 124.1 (Ar, Ar': C_(m)), 55.2 (OMe), 35.9 and 32.3 (PdCH₂ CH₂CH₂ C(O)), 29.3 and 29.1 (CHMe₂, C'HMe₂), 23.8 (PdCH₂ CH₂ CH₂ C(O)),24.5, 23.9, 23.2 and 22.5 (CHMeMe', C'HMeMe'); IR (CH₂ Cl₂) 1640 cm⁻¹ν(C(O))!. 5'(H,Me): ¹³ C NMR (CD₂ Cl₂, 100 MHz, rt) δ193.2 (C(O)). Anal.Calcd for (C₆₃ H₅₇ BF₂₄ N₂ O₂ Pd): C, 52.28; H, 3.97; N, 1.94. Found: C,52.08; H., 3.75; N, 1.61.

Example 329

The above synthesis using (2,6-i-PrPh)₂ DABMe₂ !PdMeCl (634 mg, 1.13mmol), NaBAF (1.00 g, 1.13 mmol), and MA (112 μL, 1.1 equiv) wasfollowed. The reaction mixture was stirred for 2 days and the productwas recrystallized from CH₂ Cl₂ at -30° C. to give 956 mg of orangecrystals (57.3%, 2 crops). The crystals consisted of a mixture of 6b(Me)(87%), 5'b(Me) (11.5%), and 5b(Me) (1.5%), according to ¹ H NMRspectroscopy. 6b(Me): ¹ H NMR (CD₂ Cl₂, 400 MHz, rt) δ7.43-7.26 (m, 6,H_(aryl)), 3.03 (s, 3, OMe), 2.95 (septet, 2, J=6.79, CHMe₂), 2.93(septet, 2, J=6.83, C"HMe₂), 2.39 (t, 2, J=5.86, CH₂ C(O)), 2.22 and2.20 (N═C(Me)--C'(Me)═N), 1.41 (t, 2, J=5.74, PdCH₂), 1.37, 1.30, 1.25and 1.21 (s, 6 each, J=6.80-6.94, CHMeMe', C'HMeMe'), 0.66 (pentet, 2,J=5.76, PdCH₂ CH₂ CH₂ C(O)); ¹³ C NMR (CD₂ Cl₂, 100 MHz, rt) δ183.4(C(O)), 178.7 and 171.6 (N═C--C'═N), 140.8 and 140.5 (Ar, Ar':C_(ipso)), 138.6 and 138.0 (Ar, Ar': C_(o)), 129.3 and 128.3(Ar, Ar':C_(p)), 124.9 and 124.4 (Ar, Ar': C_(m)), 54.9 (OMe), 35.8 and 30.3(PdCH₂ CH₂ CH₂ C(O)), 29.5 and 29.2 (CHMe₂, C'HMe₂), 23.7 (PdCH₂ CH₂ CH₂C(O)), 23.91, 23.86, 23.20 and 23.14 (CHMeMe', C'HMeMe'), 21.6 and 19.9(N═C(Me)--C'(Me)═N); IR (CH₂ Cl₂) 1643 cm⁻¹ ν(C(O))!. 5'b(Me): ¹ H NMR(CD₂ Cl₂, 400 MHz, rt) δ3.47 (s, 3, OMe), 2.54 (m, 1, CHMeC(O)), 2.19and 2.18 (s, 3 each, N═C(Me)--C'(Me)═N), 1.02 (d, 3, J=7.23, CHMeC(O));¹³ C NMR (CD₂ Cl₂, 100 MHz, rt) δ194.5 (C(O)), 179.2 and 172.2(N═C--C'═N), 55.6 (OMe), 44.3 (CHMeC(O)), 28.4 (PdCH₂), 21.2 and 19.6(N═C(Me)--C'(Me)═N), 18.1 (CHMeC(O)). 5b(Me): ¹ H NMR (CD₂ Cl₂, 400 MHz,rt) δ0.26 (d, 3, PdCHMe). Anal. Calcd for (C₆₅ H₆₁ BF₂₄ N₂ O₂ Pd): C,52.92; H, 4.17; N, 1.90. Found: C, 52.91; H, 4.09; N, 1.68.

Example 330

The above synthesis was followed using (2,6-i-PrPh)₂ DABAn!PdMeCl (744mg, 1.13 mmol), NaBAF (1.00 g, 1.13 mmol), and MA (112 μL, 1.1 equiv).The reaction mixture was stirred for 2 days and the product wasrecrystallized from CH₂ Cl₂ at -30° C. to give 600 mg (33.8%, 2 crops)of a mixture of 6c(Me) (85%), 5'c(Me) (8%), 5"c(Me) (6%),and 5c(Me)(1%), according to ¹ H NMR spectroscopy. 6c(Me): ¹ H NMR (CD₂ Cl₂) 400MHz, rt) δ8.17 (d, 1, J=8.37, An: H_(p)), 8.15 (d, 1, J=3.49, An':H'_(p)), 7.62-7.40 (m, 8, An, An': H_(m), H'_(m) ; Ar: H_(m), H_(p) ;Ar': H'_(m), H'_(p)), 7.08 (d, 1, J=7.19, An: H_(o)), 6.60 (d, 1,J=7.44, An': H'_(o)), 3.37 (septet, 2, J=6.79, CHMe₂), 3.33 (septet, 2,J=6.86, C'HMe₂), 2.55 (t, 2, J=5.93, CH₂ C(O)), 1.79 (t, 2, J=5.66,PdCH₂), 1.45,1.42, 1.13 and 1.02 (d, 6 each, J=6.79-6.90, CHMeMe',C'HMeMe'), 0.80 (pentet, 2, J=5.82, PdCH₂ CH₂ CH₂ C(O)); ¹³ C NMR (CD₂Cl₂, 100 MHz, rt) δ183.5 (C(O)), 175.3 and 168.7 (N═C--C'═N), 145.9 (An:quaternary C), 141.3 and 140.5 (Ar, Ar': C_(ipso)), 139.7 and 138.4 (Ar,Ar': C_(o)), 133.3 and 132.6 (An: CH),131.9 (An: quaternary C), 129.8,129.7, 129.6 and 128.5 (Ar, Ar': C_(p) ;An: CH), 126.44 and 125.8 (An:quaternary C), 126.4 and 125.6 (An: CH), 125.5 and 124.6 (Ar, Ar':C_(m)), 55.0 (OMe), 35.9 and 31.3 (PdCH₂ CH₂ CH₂ C(O)), 29.7 and 29.4(CHMe₂, C'HMe₂), 24.1 (PdCH₂ CH₂ CH₂ C(O)), 24.1, 23.8, 23.32 and 23.27(CHMeMe',C'HMeMe'); IR (CH₂ Cl₂) 1644 cm⁻¹ ν(C(O))!. 5'c(Me): ¹ H NMR(CD₂ Cl₂, 400 MHz, rt) δ3.64 (s, 3, OMe), 2.70 (m, 1, CHMeC(O)); ¹³ CNMR (CD₂ Cl₂, 100 MHz, rt) δ192.8 (C(O)). 5"c(Me): ¹ H NMR (CD₂ Cl₂, 400MHz, rt) δ3.67 (s, 3, OMe), 2.46 (t, 2, J=6.99, CH₂ C(O)), 1.72 (t, 2,J=7.04, PdCH₂). 5c(Me): ¹ H NMR (CD₂ Cl₂, 400 MHz, rt) δ0.44 (d, 3,PdCHMe).

Anal. Calcd for (C₇₃ H₆₁ BF₂₄ N₂ O₂ Pd): C, 55.80;H, 3.91; N, 1.78.Found: C, 55.76; H, 3.82; N, 1.62.

Example 331

The above synthesis was followed using (2,6-i-PrPh)₂ DABH₂ !PdMeCl (509mg, 0.954 mmol), NaBAF (845 mg, 0.953 mmol), and t-BuA (154 μL, 1.1equiv). The reaction mixture was stirred for 1 day and yielded an orangepowder (1.24 g, 87.3%) that was composed of a mixture of 6a(t-Bu) (50%),5'a(t-Bu) (42%), and 5a(t-Bu) (8%), according to ¹ H NMR spectroscopy.6a(t-Bu): ¹ H NMR (CD₂ Cl₂, 400 MHz, rt) δ8.27 and 8.25(N═C(H)--C'(H)═N), 7.45-7.20 (m, 6, H_(aryl)), 3.20 and 3.11 (septet, 2each, J=6.9, CHMe₂ and C'HMe₂), 2.42 (t, 2, J=5.9, CH₂ C(O)), 1.77 (t,2, J=5.3, PdCH₂), 1.39, 1.36, 1.22 and 1.21 (d, 6 each, J=6.7, CHMeMe'and C'HMeMe'), 1.01 (s, 9, OCMe₃), 0.68 (pentet, 2, J=6.1, PdCH₂ CH₂ CH₂C(O)); ¹³ C NMR (CD₂ Cl₂, 100 MHz, rt, excluding Ar resonances) δ182.6(C(O)), 88.8 (OCMe₃), 37.8, 33.6 and 23.9 (PdCH₂ CH₂ CH₂ C(O)), 29.3 and29.0 (CHMe₂, C'HMe₂), 27.8 (OCMe₃), 24.8, 24.5, 22.7 and 22.6 (CHMeMe',C'HMeMe'); IR (CH₂ Cl₂) 1615 cm⁻¹ ν(C(O))!; 5'a(t-Bu): ¹ H NMR (CD₂ Cl₂,400 MHz, rt; excluding Ar and i-Pr resonances) δ8.29 and 8.22 (s, 1each, N═C(H)--C'(H)═N), 2.53 (q, 1, J=7.3, C(H) (Me)C(O)), 1.75 (d, 1,J=8.9, PdCHH'), 1.53 (dd, 1, J=9.0, 7.0, PdCHH'), 1.16 (OCMe₃); ¹³ C NMR(CD₂ Cl₂, 100 MHz, rt; excluding Ar resonances) δ194.0 (C(O)), 90.6(OCMe₃), 45.9 (CHMeC(O)), 30.0 (PdCH₂), 29.4, 29.3, 29.1 and 29.1

(CHMe₂, C'HMe₂, C"HMe₂, C'"HMe₂), 27.7 (OCMe₃), 24.6, 24.4, 23.81,23.79, 23.3, 23.3, 22.62 and 22.58 (CHMeMe', C'HMeMe', C"HMeMe',C'"HMeMe'), 18.7 (CHMeC(O)); IR (CH₂ Cl₂) 1577 cm⁻¹ ν(C(O))!. 5a(t-Bu):¹ H NMR (vide infra); ¹³ C NMR(CD₂ Cl₂, 100 MHz, rt) δ190.4 (C(O)),166.7 and 160.7 (N═C--C'═N), 48.1 (CH₂ C(O)), 35.3 (PdCHMe). Anal. Calcdfor (C₆₆ H₆₃ BF₂₄ N₂ O₂ Pd): C, 53.22; H, 4.26; N, 1.88. Found: C,53.55; H, 4.20; N, 1.59.

Example 332

The above synthesis using (2,6-i-PrPh)₂ DABMe₂ !PdMeCl (499 mg, 0.889mmol), NaBAF (786 mg, 0.887 mmol), and t-BuA (145 μL, 1.1 equiv) wasfollowed. The reaction mixture was stirred for 1 day to yield an orangepowder (1.24 g, 91.8%) that consisted of a mixture of 6b(t-Bu) (26%),5'b(t-Bu) (63%), and 5b(t-Bu) (11%), according to ¹ H NMR spectroscopy.¹ H NMR (CD₂ Cl₂, 300 MHz, rt; diagnostic resonances only) 6b(t-Bu):δ2.35 (t, 2, J=6.1, CH₂ C(O)), 0.97 (s, 9, OCMe₃), 0.60 (pentet, 2,J=5.7, PdCH₂ CH₂ CH₂ C(O)); 5'b(t-Bu): δ2.43 (q, 1, J=7.2, CHMeC(O)),1.08 (s, 9, OCMe₃); 5b(t-Bu): δ0.99 (s, 9, OCMe₃), 0.29 (d, 3,J=6.74,PdCHMe); ¹³ C NMR (CD₂ Cl₂, 75 MHz, rt; diagnostic resonancesonly) 6b(t-Bu): δ182.3 (C(O)), 88.3 (OCMe₃), 37.9 and 31.9 (PdCH₂ CH₂CH₂ C(O)), 27.9 (OCMe₃), 22.0 and 20.1 (N═C(Me)--C'(Me)═N); 5'b(t-Bu):δ193.8 (C(O)), 178.8 and 171.8 (N═C--C'═N), 90.0 (OCMe₃), 45.8(CHMeC(O)), 28.7 (PdCH₂), 21.1 and 19.6 (N═C(Me)--C'(Me)═N), 18.6(CHMeC(O)); 5b(t-Bu) δ190.7 (C(O)), 48.4 (CH₂ C(O)), 33.9 (PdCHMe).Anal. Calcd for (C₆₈ H₆₇ BF₂₄ N₂ O₂ Pd): C, 53.82; H, 4.45; N, 1.85.Found: C, 53.62; H, 4.32; N, 1.55.

Example 333

The above synthesis was followed using (2,6-i-Pr-Ph)₂ DABAn!PdMeCl (503mg, 0.765 mmol), NaBAF (687 mg, 0.765 mmol), and t-BuA (125 μL, 1.1equiv). The reaction mixture was stirred for 1 day to yield an orangepowder (1.08 g, 87.8%) that consisted of a mixture of 6c(t-Bu) (47%),5'c(t-Bu) (50%), and 5c(t-Bu) (3%), according to ¹ H NMR spectroscopy. ¹H NMR (CD₂ Cl₂, 300 MHz, rt; diagnostic chelate resonances only)6c(t-Bu): δ2.48 (t, 2, J=6.05, CH₂ C(O)), 1.80 (t, 2, PdCH₂), 1.07 (s,9, OCMe₃), 0.73 (pentet, 2, J=5.87, PdCH₂ CH₂ CH₂ C(O)); 5'c(t-Bu):δ2.57 (q, 1, J=6.96, CHMeC(O)), 1.58 (dd, 1, J=8.80, 6.96, PdCHH'), 1.21(s, 9, OCMe₃); 5c(t-Bu): δ0.73 (d, 3, PdCHMe); ¹³ C NMR (CD₂Cl₂, 75 MHz,rt; diagnostic chelate resonances only) 6c(t-Bu): δ181.8 (C(O)), 87.9(OCMe₃), 37.4 and 32.2 (PdCH₂ CH₂CH₂ C(O)), 27.4 (OCMe₃); 5'c(t-Bu):δ193.0 (C(O)), 89.5 (OCMe₃), 45.5 (CHMeC(O)), 28.5 (PdCH₂), 27.2(OCMe₃), 18.1 (CHMeC(O)). Anal. Calcd for (C₇₆ H₆₇ BF₂₄ N₂ O₂ Pd): C,56.57; H, 4.19; N, 1.74. Found: C, 56.63; H, 4.06; N, 1.52.

Example 334

The above synthesis using (2,6-i-PrPh)₂ DABH₂ !PdMeCl (601 mg, 1.13mmol), NaBAF (998 mg, 1.13 mmol), and FOA (337 μL, 1.1 equiv) yieldedafter 1 day of stirring 1.21 g (59.2%) of 6a(FOA) as a red foam: ¹ H NMR(CD₂ Cl₂, 300 MHz, 0° C.) δ8.33 and 8.27 (s, 1 each, N═C(H)--C'(H)═N),7.4-7.2 (m, 6, H_(aryl)), 3.85 (t, 2, J_(HF) =13.05, OCH₂ (CF₂)₆ CF₃),3.13 and 3.08 (septet, 2 each, J=6.9, CHMe₂ and C'HMe₂), 2.65 (t, 2,J=5.62, CH₂ C(O)), 1.74 (t, 2, J=5.59, PdCH₂), 1.36, 1.29, 1.15 and 1.13(d, 6 each, J=6.73-6.82, CHMeMe', C'HMeMe'), 0.76 (pentet, 2, J=5.44,PdCH₂ CH₂ CH₂ C(O)).

Example 335

The above synthesis using (2,6-i-PrPh)₂ DABMe₂ !PdMeCl (637 mg, 1.13mmol), NaBAF (1.00 g, 1.13 mmol), and FOA (339 μL, 1.1 equiv) yieldedafter 1 day of stirring 1.36 g (65.2%) of 6b(FOA) as a yellow foam: ¹ HNMR (CD₂ Cl₂, 300 MHz, 0° C.) δ7.5-7.0 (m, 6, H_(aryl)), 3.64 (t, 2,J_(HF) =12.72, OCH₂ (CF₂)₆ CF₃), 2.90 and 2.88 (septet, 2, J=6.74, CHMe₂and C'HMe₂), 2.56 (t, 2, J=5.82, CH₂ C(O)); 2.32 and 2.22(N═C(Me)--C'(Me)═N), 1.34, 1.27, 1.23 and 1.19 (d, 6 each, J=6.75-6.82,CHMeMe', C'HMeMe'), 0.68 (pentet, 2, J=5.83, PdCH₂ CH₂ CH₂ C(O)).

Examples 336-338

The labeling scheme given in Examples 328-335 is also used here.Spectral data for the BAF counterion is the same as given in Examples328-335.

Low-Temperature NMR Observation of Methyl Acrylate Olefin ComplexFormationand Chelate Formation and Rearrangement

One equivalent of MA was added to an NMR tube containing a 0.0198Msolutionof { (2,6-iPrPh)₂ DABH₂ !PdMe(OEt₂)!}BAF in CD₂ Cl₂ (700 μL) at-78° C., and the tube was transferred to the precooled NMR probe. After14.25 min at -80° C., approximately 80% of the ether adduct had beenconverted to the olefin complex. Two setsof bound olefin resonances wereobserved in a 86:14 ratio. This observationis consistent with theexistence of two different rotamers of the olefin complex. Insertion ofMA into the Pd--Me bond occurred with predominantly 2,1 regiochemistryto give the 4-membered chelate 4a(Me) at -80° C.(t_(1/2) ˜2.0 h). Theresonances for the major rotamer of the olefin complex disappearedbefore those of the minor rotamer. Much slower conversion of 4a(Me) tothe 5-membered chelate 5a(Me) also began at -80° C. Upon warming to -60°C., complete and selective formation of 5a(Me) occurred in less than 4h. The 5-membered chelate was relatively stable at temperatures below-50° C., however, upon warming to -20° C., rearrangement to the6-membered chelate 6a(Me) was observed. NMR spectral data for the olefincomplex, 4a(Me), and 5a(Me)follow. Spectral data for 6a(Me) is identicalto that of the isolated chelate complex (see Examples 328-335).

Example 336

{ (2,6-i-PrPh)₂ DABH₂ !Pd(Me) H₂ C═CHC(O)OMe!}BAF. ¹ H NMR (CD₂ Cl₂,-80° C., 400 MHz) Major Rotamer: δ8.45 and 8.32 (s, 1 each,N═C(H)--C'(H)═N), 7.5-7.1 (m, 6, H_(aryl)), 5.14 (d, J=15.2, HH'C═),4.96 (dd, J=14.9, 8.6, ═CHC(O)), 4.63 (d, J=8.5, HH'C═), 3.68 (s, 3,OMe), 3.03, 2.90, 2.80 and 2.67 (septet, 1 each, CHMe₂, C'HMe₂, C"HMe₂,C'"HMe₂), 1.5-1.0 (doublets, 24, CHMe₂), 0.61 (s, 3, PdMe); MinorRotamer: δ8.25 and 8.18 (s, 1 each, N═C(H)--C'(H)═N), 5.25 (d, 1,HH'C═), 4.78 (dd, 1, ═CHC(O)), 4.58 (d, 1, HH'C═),3.63 (OMe).

Example 337

{ (2,6-i-PrPh)₂ DABH₂ !Pd CHEtC(O)OMe!}BAF 4a(Me). ¹ H NMR (CD₂ Cl₂, 400MHz, -60° C.) δ8.25 and 8.22 (N═C(H)--C'(H)═N), 7.5-7.2 (m, 6,H_(aryl)), 3.74 (s, 3, OMe), 3.55, 3.27, 3.08 and 2.76 (m, 1 each,CHMe₂, C'HMe₂, C"HMe₂, C'"HMe₂), 2.62 (dd, J=10.8, 2.9, CHEt), 1.4-1.0(doublets, 24, CHMe₂), 0.79 and -0.49 (m, 1 each, CH(CHH'Me)), 0.71 (t,3, J=6.6, CH(CHH'Me)).

Example 338

{ (2,6-i-PrPh)₂ DABH₂ !Pd CHMeCH₂ C(O)OMe!}BAF 5a(Me). ¹ H NMR (CD₂ Cl₂,400 MHz, -60° C.) δ8.24 and 8.21 (N═C(H)--C'(H)═N), 7.4-7.2 (m, 6,H_(aryl)), 3.59 (s, 3, OMe), 3.47, 3.32, 2.98 and 2.81 (septet, 1 each,CHMe₂, C'HMe₂, C"HMe₂, C'"HMe₂), 3.08 (dd, 1, J=18.4, 7.3, CHH'C(O)),1.74 (pentet, 1, J=6.9, PdCHMe), 1.60 (d, 1, J=18.6, CHH'C(O)), 1.34 (d,6, J=5.6, C'HMeMe' and C'"HMeMe'), 1.32 (d, 3, J=6.2, CHMeMe'), 1.24 (d,3, J=6.8, C"HMeMe'), 1.18 (d, 6, J=6.8, C'HMeMe' and C"HMeMe'), 1.15 (d,3, J=6.8, C'"HMeMe'), 1.08 (d, 3, CHMeMe'), 0.35 (d, 3, J=6.9, PdCHMe);¹³ C NMR (CD₂ Cl₂, 100 MHz, -80° C.) δ190.5 (C(O)), 166.1 (J_(CH) =181,N═C(H)), 160.7 (J_(CH) =181, N═C'(H)), 142.8 and 141.6 (Ar, Ar':C_(ipso)), 139.0, 138.6, 138.2 and 137.7 (Ar: C_(o), C_(o) ' and Ar':C_(o), C_(o) '), 128.8 and 128.2 (Ar, Ar': C_(p)), 124.1, 123.54,123.48, 123.4 (Ar: C_(m), C_(m) ' and Ar': C_(m), C_(m) '), 55.5 (OMe),45.1 (CH₂ C(O)), 35.6 (PdCHMe), 28.8, 28.5, 28.1 and 27.8 (CHMe₂,C'HMe₂, C"HMe₂, C'"HMe₂), 25.6, 24.2, 23.1, 23.0, 22.7, 22.3, 21.9,21.3, and 21.3 (CHMeMe', C'HMeMe', C"HMeMe', C'"HMeMe' and PdCHMe).

Example 339-342

The labeling scheme given in Examples 328-335 is also used for Examples339-342. Spectral data for the BAF counterion is the same as given inExamples 328-335.

Low-Temperature NMR Observation of t-Butyl Acrylate Olefin ComplexFormation and Chelate Formation and Rearrangement

One equiv of t-BuA was added to an NMR tube containing a 0.0323Msolution of { (2,6-i-PrPh)₂ DABH₂ !PdMe(OEt₂)}BAF in CD₂ Cl₂ (700 μL) at-78° C., and the tube was transferred to the precooled NMR probe. Theolefin complex was observed at -80° C., and the probe was then warmed to-70° C. After 1 h at -70° C., conversion to 5a(t-Bu) and 5'a(t-Bu) wasalmost complete, with small amounts (<10%) of the olefin complex and4a(t-Bu) still present. Conversion of 5a(t-Bu) to 6a(t-Bu) was followedat -10° C.(t_(1/2) ˜1 h). When this experiment was repeated using 5equiv of t-BuA, conversion to 5a, 5'a and 6a was observed at -80° C.After allowing the solution to stand at rt for 5 days, partialconversion to theunsubstituted 5-membered chelate 5"a(t-Bu) wasobserved. Spectral data for the olefin complex, 4a(t-Bu), 5a(t-Bu) and5"a(t-Bu) follow. Spectral datafor 5'a(t-Bu) and 6a(t-Bu) are identicalto that of the isolated chelate complexes (see Examples 328-335).

Example 339

{ (2,6-i-PrPh)₂ DABH₂ !PdMe H₂ C═CHC(O)O-t-Bu!}BAF. ¹ H NMR (CD₂ Cl₂,400 MHz, -80° C.) δ8.45 and 8.30 (s, 1 each N═C(H)--C'(H)═N), 7.4-7.2(m, 6, H_(aryl)), 5.15(d, 1, J=15.3, HH'C═), 4.89 (dd, 1, J=14.7, 8.4,═CHC(O)), 4.61 (d,1, J=7.7, HH'C═), 2.92, 2.90, 2.80 and 2.64 (septets,1 each, CHMe₂, C'HMe₂), C"HMe₂ and C'"HMe₂), 1.31 (s, 9, OCMe₃), 1.5-0.8(doublets, 24, CHMe₂), 0.60 (s, 3, PdMe).

Example 340

{ (2,6-i-PrPh)₂ DABH₂ !Pd CHEtC(O)O-t-Bu!}BAF 4a(t-Bu). ¹ H NMR (CD₂Cl₂, 400 MHz, -70° C.) δ8.22 and 8.21 (s, 1 each, N═C(H)--C'(H)═N), 2.21(d, 1, J=9.2, PdCHEt), 0.71 (t, 3, J=7.9, PdCH(CH₂ Me)), 0.5 and -0.4(br m, 1 each, PdCH(CHH'Me)).

Example 341

{ (2,6-i-PrPh)₂ DABH₂ !Pd CHMeCH₂ C(O)O-t-Bu!}BAF 5a(t-Bu). ¹ H NMR (CD₂Cl₂, 400 MHz, -40° C.) δ8.28 and 8.24 (s, 1 each, N═C(H)--C'(H)═N),7.4-7.2 (m, 6, H_(aryl)), 3.44, 3.32, 2.96 and 2.86 (septet, 1 each,CHMe₂, C'HMe₂, C"HMe₂, C'"HMe₂), 2.94 (dd, 1, J=18.6, 7.1, CHH'C(O)),1.79 (pentet, 1, J=6.7, PdCHMe), 1.62 (d, 1, J=18.5, CHH'C(O)), 1.4-1.0(doublets, 24, CHMe₂), 1.10 (s, 9, OCMe₃), 0.22 (d, 3, J=6.9, PdCHMe).

Example 342

{ 2,6-i-PrPh)₂ DABH₂ !Pd CH₂ CH₂ C(O)O-t-Bu!}BAF 5"a(t-Bu). ¹ H NMR (CD₂Cl₂, 400 MHz, rt) δ2.40 (t, 2, J=7.0, CH₂ (O)), 1.65 (t, 2, J=7.0,PdCH₂).

Example 343

The labeling scheme given in Examples 328-335 is also used for Example343.Spectral data for the BAF counterion is the same as given inExamples 328-335.

Low-Temperature NMR Observation of FOA Chelate Formation andRearrangement

One equiv of FOA was added to an NMR tube containing a 0.0285M solutionof { (2,6-i-PrPh)₂ DABH₂ !PdMe(OEt₂)}BAF (1a) at -78° C. in CD₂ Cl₂ (700μL), and the tube was briefly shaken at this temperature. A ¹ H NMRspectrum at -80° C. showed that FOA was not dissolved. The sample wasallowed to warm slightly as it was shaken again and another spectrum wasthen acquired at -80° C. Approximately equal amounts of 5a(FOA) and6a(FOA) were observed along with small amounts of the ether adduct 1aand FOA (an olefin complex was not observed). Rearrangement of 5a(FOA)to 6a(FOA) was observed at -40° C. and was complete upon warming to -30°C. NMR spectral data for 5a(FOA) follow. Spectral data for 6a(FOA) areidentical with that of the isolated complex (vide supra).

{ (2,6-i-PrPh)₂ DABH₂ !Pd CHMeCH₂ C(O)OCH₂ (CF₂)₆ CF₃ !}BAF 5a(FOA). ¹ HNMR (CD₂ Cl₂, 300 MHz, -40° C.) δ8.23 and 8.22 (s, 1 each,N═C(H)--C'(H)═N), 3.47 (t, 2, J_(HF) =13.38, OCH₂ (CF₂)₆ CF₃), 3.20 (dd,1, J=19.25, 7.28, CHH'C(O)), 2.58 (pentet, 1, J=6.99, PdCHMe), 1.77 (d,1, J=19.81, CHH'C(O)), 0.33 (d, 3, J=6.88, PdCHMe). Spectral data forthe BAF counterion is the same as givenin Examples 328-335.

Example 344

NMR Observation of { (2,6-i-PrPh)₂ DABH₂ !Pd CHR"CH₂ CH₂ C(O)OMe!}BAFand { (2,6-i-PrPh)₂ DABH₂ !Pd CH₂ CH₂ C(O)OMe!}BAF. A solution of {(2,6-i-PrPh)₂ DABH₂ !PdMe(OEt₂)}BAF (21.5 mg, 0.0150 mmol) in 700 μL ofCD₂ Cl₂ was prepared at -78° C. Ethylene (5 equiv) was added viagastight syringe and the tube was shaken briefly to dissolve theethylene.Methyl acrylate (5 equiv) was then added to the solution, alsovia gastightmicroliter syringe, and the tube was shaken briefly again.The tube was transferred to the NMR probe, which was precooled to -80°C. Resonances consistent with the formation of the ethylene adduct {(2,6-i-PrPh)₂ DABH₂ !PdMe(H₂ C═CH₂)}BAF were observed. The solution waswarmed and ethylene insertion was monitored at -40° to -20° C. Theconsumption of one equiv of methyl acrylate occurred as the last equivof ethylene disappeared, and resonances consistent with the formation ofa substituted 6-membered chelate complex { (2,6-i-PrPh)₂ DABH₂ !PdCHR"CH₂ CH₂ C(O)OMe!}BAF were observed 8.30 and 8.29 (N═C(H)--C'(H)═N),3.17 (OMe)!. The large upfield shift of the methoxy resonance isparticularly diagnostic for formation of the 6-membered chelate complexin these systems. The substituted 6-membered chelate complex wasobserved at -20° C. and initially upon warming to RT. After 2 h at RT,decomposition of the substituted 6-membered chelate complex had begun.After 24 h at RT, an additional 0.5 equiv of MA had been consumed andtriplets at 2.42 and 1.66 ppm, consistent with the formation of theunsubstituted 5-membered chelate complex { (2,6-i-PrPh)₂ DABH₂ !Pd CH₂CH₂ C(O)OMe!}BAF, were observed. Spectral data for the BAF counterion isthe same as given in Examples 328-335.

Example 345

NMR Observation of { (2,6-i-PrPh)₂ DABMe₂ !Pd(CHR"CH₂ CH₂ C(O)OMe!}BAF.The procedure of Example 344 was followed with analogous results, e.g.,resonances for the formation of a substituted 6-membered chelate complex{ (2,6-i-PrPh)₂ DABMe₂ !Pd CHR"CH₂ CH₂ C(O)OMe!}BAF were observedfollowing complete ethylene consumption 3.03 (s, OMe), 3.12, 2.96, 2.89,2.83 (septets, CHMe₂, C'HMe₂, C"HMe₂ and C'"HMe₂), 2.23 and 2.19 (s,N═C(Me)--C'(Me)═N)!. Again, the large upfield shift of themethoxyresonance is diagnostic for the formation of the six-memberedchelate complex. The observation of four i-propyl methine resonances(vs. two i-propyl methine resonances in the unsubstituted six-memberedchelate complex) reflects the asymmetry introduced in the molecule dueto the introduction of the R" substituent on C.sub.α of the chelate ringand further supports the proposed structure. Spectral data for the BAFcounterion is the same as given in Examples 328-335.

Example 346

{ (2,6-i-PrPh)₂ DABH₂ !Pd(H₂ C═CH₂) CH₂ CH₂ CH₂ C(O)OMe!}BAF. Ethylenewas transferred at -78° C.via gastight microliter syringe to an NMR tubecontaining a CD₂ Cl₂ solution of the chelate complex { (2,6-i-PrPh)₂DABH₂ !Pd CH₂ CH₂ CH₂ C(O)OMe!}BAF. NMR data for the ethylene complexfollow; it was observed in equilibrium with the starting chelatecomplex: ¹ HENMR (CD₂ Cl₂, 300 MHz, 182° K) δ8.30 and 8.29 (s, 1 each,N═C(H)--C'(H)═N), 7.36-7.24 (m, 6, H_(aryl)), 3.72 (s, 3, OMe), 3.43 (brs, 4, H₂ C═CH₂), 3.10 (m, 2, CHMe₂), 2.70 (m, 2, C"HMe₂), 2.20 (m, 2,CH₂ C(O)), 1.25, 1.16, 1.09 and 1.07 (d, 6 each, J=7, CHMeMe',C'HMeMe'), 1.20(PdCH₂ (obscured by CHMeMe' peaks, observed byH,H--COSY)), 0.56 (m, 2, PdCH₂ CH₂ CH₂ C(O)); ¹³ C NMR (CD₂ Cl₂, 400MHz, -80° C.) δ178.9 (C(O)), 162.7 (J_(CH) =179, N═C), 162.5 (J_(CH)=179, N═C'), 141.3 and 140.5 (Ar, Ar': C_(ipso)), 138.5 and 138.1 (Ar,Ar': CO), 128.5 and 128.3 (Ar, Ar': C_(p)), 124.1 and 124.0 (Ar, Ar':C_(o)), 122.9 (J_(CH) =159.3, freeH₂ C═CH₂), 70.2 (J_(CH) =158.6, boundH₂ C═CH₂), 53.0 (OMe), 36.5, 33.0 and 22.6 (PdCH₂ CH₂ CH₂ C(O)), 27.8(CHMe₂, C'HMe₂), 25.6, 25.3, 22.1 and 21.4 (CHMeMe', C'HMeMe'). Spectraldata for the BAF counterion is the same as given in Examples 328-335.

Example 347

{ (2,6-i-PrPh)₂ DABMe₂ !Pd(H₂ C═CH₂) (CH₂ CH₂ CH₂ C(O)OMe!}BAF. Ethylenewas transferred at -78° C.via gastight microliter syringe to an NMR tubecontaining a CD₂ Cl₂ solution of the chelate complex { (2,6-i-PrPh)₂DABMe₂ !Pd CH₂ CH₂ CH₂ C(O)OMe!}BAF. NMR data for the ethylene complexfollow; even at low temperature and in the presence of a large excess ofethylene, this complex could only be observed in the presence ofat leastan equimolar amount of the corresponding six-membered chelate: ¹ HENMR(CD₂ Cl₂, 300 MHz, 172° K): δ7.35-7.19(m, 6, H_(aryl)), 4.31 (br s, 4,H₂ C═CH₂), 3.45 (s, 3, OMe), 2.73-2.54 (m, 4, CHMe₂), 2.38 and 2.22 (s,3 each, N═C(Me)--C'(Me)═N), 1.64 (m, 2, CH₂ C(O)), 1.02 (d, 6, J=6,CHMeMe"). From the available H,H--COSY data the remaining PdCH₂ CH₂ CH₂C(O)-- and CHMe-signals could not be unambiguously assigned, due to thepresence of the six-membered chelate. Spectral data for the BAFcounterion is the same as given in Examples 328-335.

Example 348

{ (2,6-i-PrPh)₂ DABAn!Pd(H₂ C═CH₂) CH₂ CH₂ CH₂ C(O)OMe!}BAF. Ethylenewas transferred at -78° C. via gastight microliter syringe to an NMRtube containing a CD₂ Cl₂ solution of the chelate complex {(2,6-i-PrPh)₂ DABAn!Pd(CH₂ CH₂ CH₂ C(O)OMe)!BAF. NMR data for theethylene complex follow; it was observed in equilibrium with thestarting chelate complex: ¹ HNMR (CD₂ Cl₂, 300 MHz, 178° K): δ8.06 and8.02 (d, J=8, 1 each, An and An': H_(p) and H'_(p)), 7.50-7.38 (m, 8, Anand An': H'_(m) and H_(m), Ar: H_(m) and H_(p)), 6.48 (d, J=7, 2, An andAn': H_(o) and H'_(o)), 4.56 (br s, 4, H₂ C═CH₂), 3.45 (s, 3, OMe), 2.99and 2.91 (m, 2 each, CHMe₂ and C'HMe₂), 1.77 (m, 2, CH₂ C(O)), 1.29,1.27, 0.82 and 0.77 (d, J=6-7, 6 each, CHMeMe', C'HMeMe'). H,H--COSYreveals that the remaining PdCH₂ CH₂ CH₂ C(O)-signals are obscured bythe CHMe-signals at 1.2 ppm. Spectral data for the BAF counterion is thesame as given in Examples328-335.

Example 349 { (2,6-i-PrPh)₂ DABH₂ !Pd CH₂ CH₂ CH₂ C(O)OCH₂ (CF₂)₆ CF₃!(H₂ C═CH₂)}BAF

Ethylene (0.78 equiv) was added via gastight microliter syringe to a0.0105M solution of the chelate complex { (2,6-i-PrPh)₂ DABH₂ !Pd CH₂CH₂ CH₂ C(O)OCH₂ (CF₂)₆ CF₃ !}BAF in CD₂ Cl₂ (700 μL). NMR data for theethylene complex follow; it was observed in equilibrium with thestarting chelate complex: ¹ H NMR (CD₂ Cl₂, 300 MHz, 213.0° K) δ8.40and8.25 (N═C(H)--C'(H)═N), 7.5-7.1 (m, 6, H_(aryl)), 4.50 (t, 2, J_(HF)=13.39, OCH₂ (CF₂)₆ CF₃), 4.41 (s, 4, H₂C═CH₂), 2.94 and 2.70 (septet, 2each, CHMe₂, C'HMe₂), 1.80 (t, 3, CH₂ C(O)), 1.4-1.0 (CHMeMe', C'HMeMe',PdCH₂ CH₂ CH₂ C(O)). Spectral data for the BAF counterion is the same asgiven in Examples 328-335.

Example 350

A 12 mg (0.02 mmol) sample of (2,6-i-PrPh)₂ DABAn!NiBr₂ was placed in a25 mL high pressure cell. The reactor was purged with argon. The reactorwas cooled to 0° C. before 2 mL of a 10% MAO solution in toluene wasadded under a positive argon purge. The reactor was filled (3/4 full)with liquid CO₂ (4.5 MPa) and a 689 kPa head pressure of ethylene wasadded by continuous flow. A 6 degree exotherm was observed. Alayer ofpolyethylene formed immediately at the ethylene CO₂ interface. After 20minutes, the cell was vented and the polyethylene removed from thereactor. The polymer was dried in vacuo for several hours. Polyethylene(2.05 g) was isolated; M_(n) =597,000, M_(w) /M_(n) =2.29, T_(m) =128°C. This example demonstrates the applicability of liquid CO₂ as asolvent for polymerization in these catalyst systems.

Example 351

A 12 mg (0.02 mmol) sample of (2,6-i-PrPh)₂ DABAn!NiBr₂ was placed in a25 mL high pressure cell and the reactor was purged with argon. Thereactor was heated to 40° C. and 2 mL of a 10% MAO solution in toluenewas added. CO₂ (20.7 MPa) and ethylene (3.5 MPa, continuous flow) wasthen added to the reactor. Polyethylene began adhering to the sapphirewindow within minutes. After 20 minutes, the cellwas vented and thepolyethylene removed from the reactor. The polymer was dried in vacuofor several hours. Polyethylene (0.95 g) was isolated; M_(n) =249,000,M_(w) /M_(n) =2.69, T_(m) =113° C. This example demonstrates theapplicability of supercritical CO₂ as a solvent for polymerization inthese catalyst systems.

Example 352

A standard solution of (2,6-i-PrPh)₂ DABAn!NiBr₂ was prepared asfollows:1,2-difluorobenzene (10 mL) was added to 6.0 mg of (2,6-i-PrPh)₂DABAn!NiBr₂ (8.4×10⁻⁶ mol) in a 10 mL volumetric flask. The standardsolution was transferred to a Kontes flask and stored under an argonatmosphere.

A 1000 mL Parr® stirred autoclave under an argon atmosphere, was chargedwith 1 mL of a standard solution of (2,6-i-PrPh)₂ DABAn!NiBr₂ (8.3×10⁻⁷mol), and 200 mL of dry, deaerated toluene. The reactor was purged withethylene before addition of 2 mL of a10% MAO solution in toluene. Theautoclave was rapidly pressurized with ethylene to 1.4 MPa as theinternal temperature increased from 25° C. to 45° C. within seconds.Activation of the internal cooling system returned the reactortemperature to 30° C. After 10 minutes,the ethylene was vented andacetone and water were added to quench the reaction. Solid polyethylenewas recovered from the reactor collected and washed with 6M HCl, H₂ O,and acetone. The resulting polymer was dried under high vacuum overnightto yield 7.0 g (1.8×10⁶ TO/h)of polyethylene. Differential scanningcalorimetry: T_(m) =118° C.(133 J/g). Gel permeation chromatography(trichlorobenzene, 135° C.,polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n) =470,000; M_(w)=1,008,000; M_(w) /M_(n) =2.14. ¹³ C-NMR analysis: total methyls/1000CH₂ (27.6), methyl (21.7), ethyl (2.6), propyl (0.7), butyl (1), amyl(0.4).

Example 353

A 1000 mL Parr® stirred autoclave under an argon atmosphere, was chargedwith 1 mL of a standard solution of (2,6-i-PrPh)₂ DABAn!NiBr₂ (8.3×10⁻⁷mol), and 200 mL of dry, deaerated toluene. The reactor was purged withethylene before addition of 2 mL of a10% MAO solution in toluene. Theautoclave was rapidly pressurized with ethylene to 2.8 MPa as theinternal temperature increased from 25° C. to 48° C. within seconds.Activation of the internal cooling system returned the reactortemperature to ˜30° C. After 10 minutes, the ethylene was vented andacetone and water were added to quench the reaction. Solid polyethylenewas recovered from the reactor collected and washed with 6M HCl, H₂ O,and acetone. The resulting polymer was dried under high vacuum overnightto yield 8.85 g (2.3×10⁶ TO/h) of polyethylene. DSC: T_(m) =122° C. GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n) =485,000; M_(w)=1,042,000; M_(w) /M_(n) =2.15. ¹³ C-NMR analysis: total methyls/1000CH₂ (21.3), methyl (16.3), ethyl (2.1), propyl (0.7), butyl (0.9), amyl(0.2).

Example 354

A 1000 mL Parr® stirred autoclave under an argon atmosphere, was chargedwith 1 mL of a standard solution of (2,6-i-PrPh)₂ DABAn!NiBr₂ (8.3×10⁻⁷mol), and 200 mL of dry, deaerated toluene. The reactor was purged withethylene before addition of 2 mL of a10% MAO solution in toluene. Theautoclave was rapidly pressurized with ethylene to 4.1 MPa as theinternal temperature increased from 25° C. to 45° C. within seconds.Activation of the internal cooling system returned the reactortemperature to ˜30° C. After 10 min, the ethylene was vented and acetoneand water were added to quench the reaction. Solid polyethylene wasrecovered from the reactor collected and washed with 6M HCl, H₂ O, andacetone. The resulting polymer was dried under high vacuum overnight toyield 7.45 g (1.9×10⁶ TO/h) of polyethylene. DSC: T_(m) =126° C. GPC(trichlorobenzene,135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n) =510,000; M_(w)=1,109,000;M_(w) /M_(n) =2.17. ¹³ C-NMR analysis: total methyls/1000CH₂(5.1), methyl (5.1), ethyl (0), propyl (0), butyl (0), amyl (0).

Example 355

A 1 mg (1.7×10⁻⁶ mol) sample of (2,6-i-PrPh)₂ DABH₂ !NiBr₂ was placed ina Parr® 1000 mL stirred autoclave under argon. The autoclave was sealedand 200 mL of dry toluene was added. The reactor was purged withethylene before addition of 1.5 mL of a 10% MAO solution in toluene. Theautoclave was rapidly pressurized with ethylene to 1.4 MPa as theinternal temperature increased from 25° C. to 45° C. within seconds.Activation of the internal cooling system returned the reactortemperature to ˜30° C. After 10 min, theethylene was vented and acetoneand water were added to quench the reaction. Solid polyethylene wasrecovered from the reactor collected and washed with 6M HCl, H₂ O, andacetone. The resulting polymer was dried under high vacuum overnight toyield 14.1 g (1.8×10⁶ TO/h) of polyethylene. DSC: T_(m) =126° C. (151J/g). GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as polyethylene using universal calibration theory): M_(n)=32,000; M_(w) =89,000; M_(w) /M_(n) =2.75.

Example 356

A 1 mg (1.7×10⁻⁶ mol) sample of (2,6-i-PrPh)₂ DABH₂ !NiBr₂ was placed ina Parr® 1000 mL stirred autoclave under argon. The autoclave was sealedand 200 mL of dry toluene was added. The reactor was purged withethylene before addition of 1.5 mL of a 10% MAO solution in toluene. Theautoclave was rapidly pressurized with ethylene to 2.1 MPa as theinternal temperature increased from 25° C. to 50° C. within seconds.Activation of the internal cooling system returned the reactortemperature to ˜30° C. After 10 min, theethylene was vented and acetoneand water were added to quench the reaction. Solid polyethylene wasrecovered from the reactor collected and washed with 6M HCl, H₂ O, andacetone. The resulting polymer was dried under high vacuum overnight toyield 16.1 g (2×10⁶ TO/h) of polyethylene. DSC: T_(m) =129° C. (175J/g). GPC (trichlorobenzene, 135° C., polystyrene reference, resultscalculated as polyethylene using universal calibration theory): M_(n)=40,000; M_(w) =89,000; M_(w) /M_(n) =2.22.

Example 357

A 1.2 mg (1.9×10⁻⁶ mol) sample of (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ was placedin a Parr® 1000 mL stirred autoclave under argon. The autoclave wassealed and 200 mL of dry toluene was added. The reactor was purged withethylene before addition of 2.0 mL of a 10% MAO solution in toluene. Theautoclave was rapidly pressurized with ethylene to 1.4 MPa as theinternal temperature increased from 24° C. to 31° C. within seconds.Activation of the internal cooling system returned the reactortemperature to ˜25° C. After 12 min, the ethylene was vented and acetoneand water were added to quench the reaction. Solid polyethylene wasrecovered from the reactor collected and washed with 6M HCl, H₂ O, andacetone. The resulting polymer was dried under high vacuum overnight toyield 8 g (9×10⁵ TO/h) of polyethylene. DSC: Broad melt beginningapproximately 0° C. with a maximum at 81° C. (25 J/g). GPC(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n) =468,000; M_(w)=1,300,000; M_(w) /M_(n) =2.81. ¹³ C-NMR analysis: total methyls/1000CH₂ (46.6), methyl (37.0), ethyl (2.4), propyl (1.6), butyl (1.3), amyl(1.4).

Example 358

A 1.2 mg (1.9×10⁻⁶ mol) sample of (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ was placedin a Parr® 1000 mL stirred autoclave under argon. The autoclave wassealed and 200 mL of dry toluene was added. The reactor was purged withethylene before addition of 2.0 mL of a 10% MAO solution in toluene. Theautoclave was rapidly pressurized with ethylene to 2.8 MPa as theinternal temperature increased from 24° C. to 34° C. within seconds.After 12 min, the ethylene was vented and acetone and water were addedto quench the reaction. Solid polyethylene was recovered from thereactor collected and washed with 6M HCl, H₂ O, and acetone. Theresulting polymer was dried under high vacuum overnight to yield 6.5 g(6×10⁵ TO/h) of polyethylene. DSC: Broad melt beginning approximately60° C. with a maximum at 109° C. (80 J/g). GPC (trichlorobenzene, 135°C., polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n) =616,000; M_(w) =1,500,000; M_(w)/M_(n) =2.52. ¹³ C-NMR analysis: total methyls/1000 CH₂ (32.0), methyl(24.6), ethyl (2.6), propyl (1.3), butyl (0.6), amyl (1.3).

Example 359

A 1.2 mg (1.9×10⁻⁶ mol) sample of (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ was placedin a Parr® 1000 mL stirred autoclave under argon. The autoclave wassealed and 200 mL of dry toluene was added. The reactor was purged withethylene before addition of 2.0 mL of a 10% MAO solution in toluene. Theautoclave was rapidly pressurized with ethylene to 4.1 MPa. After 12min, the ethylene was vented and acetone and water were added to quenchthe reaction. Solid polyethylene was recovered from the reactorcollected and washed with 6M HCl, H₂ O, and acetone. The resultingpolymer was dried under high vacuum overnight to yield 7.2 g (7×10⁵TO/h) of polyethylene. GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n) =800,000; M_(w) =1,900,000; M_(w) /M_(n)=2.43. ¹³ C-NMR analysis: total methyls/1000 CH₂ (18.7), methyl (14.9),ethyl (1.7), propyl (1.1), butyl (0.3), amyl (0.4).

Example 360

A 1.5 mg (2.4×10⁻⁶ mol) sample of (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ and 200 mLof dry toluene was added to a Parr®1000 mL stirred autoclave under anargon atmosphere. The reactor was heatedto 50° C. and purged withethylene before addition of 3.0 mL of a 7%MMAO solution in heptane. Theautoclave was rapidly pressurized with ethylene to 690 kPa. After 10min, the ethylene was vented and acetone andwater were added to quenchthe reaction. Solid polyethylene was recovered from the reactorcollected and washed with 6M HCl, H₂ O, and acetone.The resultingpolymer was dried under high vacuum overnight to yield 6.25 g(6×10⁵TO/h) of polyethylene. DSC: Broad melt beginning approximately -25° C.with a maximum at 50° C.; T_(g) =-36° C. GPC (trichlorobenzene, 135° C.,polystyrene reference, results calculated as polyethylene usinguniversal calibration theory): M_(n) =260,000; M_(w) =736,000; M_(w)/M_(n) =2.83.

Example 361

A 1.5 mg (2.4×10⁻⁶ mol) sample of (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ and 200 mLof dry toluene was added to a Parr®1000 mL stirred autoclave under anargon atmosphere. The reactor was heatedto 65° C. and purged withethylene before addition of 3.0 mL of a 7%MMAO solution in heptane. Theautoclave was rapidly pressurized with ethylene to 690 kPa. After 10min, the ethylene was vented and acetone andwater were added to quenchthe reaction. Solid polyethylene was recovered from the reactorcollected and washed with 6M HCl, H₂ O, and acetone.The resultingpolymer was dried under high vacuum overnight to yield 7.6 g (7×10⁵TO/h) of polyethylene. DSC: Broad melt beginning approximately -50° C.with a maximum at 24° C. GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n) =176,000; M_(w) =438,000; M_(w) /M_(n) =2.49.

Example 362

A 1.5 mg (2.4×10⁻⁶ mol) sample of (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ and 200 mLof dry toluene was added to a Parr®1000 mL stirred autoclave under anargon atmosphere. The reactor was heatedto 80° C. and purged withethylene before addition of 3.0 mL of a 7%MMAO solution in heptane. Theautoclave was rapidly pressurized with ethylene to 690 kPa. After 10min, the ethylene was vented and acetone andwater were added to quenchthe reaction. Solid polyethylene was recovered from the reactorcollected and washed with 6M HCl, H₂ O, and acetone.The resultingpolymer was dried under high vacuum overnight to yield 1.0 g (0.9×10⁵TO/h) of polyethylene. DSC: Broad melt beginning approximately -50° C.with a maximum at -12° C. GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n) =153,000; M_(w) =273,000; M_(w) /M_(n) =1.79.

Example 363

A 1.5 mg (2.4×10⁻⁶ mol) sample of (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ and 200 mLof dry toluene was added to a Parr®1000 mL stirred autoclave under anargon atmosphere. The reactor was heatedto 80° C. and purged withethylene before addition of 3.0 mL of a 7%MMAO solution in heptane. Theautoclave was rapidly pressurized with ethylene to 2.1 MPa. After 10min, the ethylene was vented and acetone andwater were added to quenchthe reaction. Solid polyethylene was recovered from the reactorcollected and washed with 6M HCl, H₂ O, and acetone.The resultingpolymer was dried under high vacuum overnight to yield 1.05 g(0.9×10⁵TO/h) of polyethylene. DSC: Broad melt beginning approximately -25° C.with a maximum at 36° C.

Example 364

A standard solution of (2,6-i-PrPh)₂ DABAn!NiBr₂ was prepared asfollows:1,2-difluorobenzene (10 mL) was added to 6.0 mg of (2,6-i-PrPh)₂DABAn!NiBr₂ (8.4×10⁻⁶ mol) in a 10 mL volumetric flask. The standardsolution was transferred to a Kontes flask and stored under an argonatmosphere.

A 250 mL Schlenk flask was charged with 1 mL of a standard solution of(2,6-i-PrPh)₂ DABAn!NiBr₂ (8.3×10⁻⁷ mol), and 100 mLof dry, deaeratedtoluene. The flask was cooled to -20° C. in a dry ice isopropanol bathand filled with ethylene (100 kPa, absolute) before addition of 1.5 mLof a 10% MAO solution in toluene. After 30 min, acetoneand water wereadded to quench the reaction. Solid polyethylene was recovered from theflask collected and washed with 6M HCl, H₂ O, and acetone. The resultingpolymer was dried under high vacuum overnight to yield 0.8 g (7×10⁴TO/h) of polyethylene. GPC (trichlorobenzene, 135° C., polystyrenereference, results calculated as polyethylene using universalcalibration theory): M_(n) =519,000; M_(w) =768,000; M_(w) /M_(n) =1.48.

Example 365

A 250 mL Schlenk flask was charged with 20 mg of (2,6-i-PrPh)₂ DABMe₂!NiBr₂ (3.2×10⁻⁵ mol), and 75 mL of dry, deaerated toluene. The flaskwas cooled to 0° C. filled with propylene (100 kPa absolute) beforeaddition of 1.5 mL of a 10% MAO solution in toluene. After 30 min,acetone and water were added to quench the reaction. Solid polypropylenewas recovered from the flask and washed with 6M HCl, H₂ O, and acetone.The resulting polymer was dried underhigh vacuum overnight to yield 0.15g polypropylene. DSC: T_(g) =-31° C. GPC (trichlorobenzene, 135° C.,polystyrene reference): M_(n) =25,000; M_(w) =37,000; M_(w) /M_(n)=1.47.

Example 366

Cyclopentene (16 μL, 10 eq) was added to a suspension of (2,6-i-PrPh)₂DABAn!NiBr₂ (12 mg, 1.6×10⁻⁵ mol) in 50 mL of dry toluene. A 10% MAOsolution (1.5 mL) in toluene was added andthe homogenous mixture stirredfor 2 h at 25° C. After 2 h, the flask was filled with ethylene (100kPa, absolute) and the reaction stirred for 15 min. Acetone and waterwere added to quench the polymerization and precipitate the polymer.Solid polyethylene was recovered from the flask collected and washedwith 6M HCl, H₂ O, and acetone. The resulting polymer was dried underhigh vacuum overnight to yield 3.6 g (32,000 TO/h) polyethylene. GPC:(trichlorobenzene, 135° C., polystyrene reference, results calculated aspolyethylene using universal calibration theory): M_(n) =87,000; M_(w)=189,000; M_(w) /M_(n) =2.16. A control experiment was run underidentical conditions to that described above except no cyclopentene wasadded to stabilize the activated nickel complex. Polyethylene (380 mg,3500 TO/h) was isolated. This example demonstrates the applicability ofthe Ni agostic cation as a potential soluble stable initiator for thepolymerization of ethylene and other olefin monomers.

Example 367

1-Hexene (3 mL, 6 vol %) was added to a suspension of (2,6-i-PrPh)₂DABAn!NiBr₂ (12 mg, 1.6×10⁻⁵ mol) in 50 mL of dry toluene.The flask wascooled to -20° C. in a dry ice isopropanol bath and 1.5 mL of a 10% MAOsolution in toluene was added. After stirring the reaction for 1.5 h,acetone and water were added to quench the polymerization andprecipitate the polymer. Solid poly(1-hexene) was recovered from theflask collected and washed with 6M HCl, H₂ O, and acetone. The resultingpolymer was dried under high vacuum overnight to yield 200 mgpoly(1-hexene). GPC (trichlorobenzene, 135° C., polystyrene reference):M_(n) =44,000; M_(w) =48,000; M_(w) /M_(n) =1.09.

Example 368

1-Hexene (2.5 mL, 6 vol %) was added to a suspension of(2,6-i-PrPh)₂DABAn!NiBr₂ (6 mg, 8.3×10⁻⁶ mol) in 50 mL of dry toluene.The flask was cooled to -10° C. in a dry ice isopropanol bath and 1.5 mLof a 7% MMAO solution in heptane was added. After stirring the reactionfor 1 h, acetone and water were added to quench the polymerization andprecipitate the polymer. Solid poly(1-hexene) was recovered from theflask and washed with 6M HCl, H₂ O, and acetone. The resulting polymerwas dried under high vacuum overnight to yield 250 mg poly(1-hexene).GPC (dichloromethane, polystyrene reference): M_(n) =51,000; M_(w)=54,000; M_(w) /M_(n) =1.06.

Example 369

Propylene (1 atm) was added to a Schlenk flask charged with a suspensionof (2,6-i-PrPh)₂ DABAn!NiBr₂ (12 mg, 1.7×10⁻⁵ mol) in 50 mL of drytoluene after cooling the mixture to -15° C. in a dry ice isopropanolbath. A 7% MMAO solution in heptane was added. After stirring thereaction for 30 min, acetone and water were added to quench thepolymerization and precipitate the polymer. Solid polypropylene wasrecovered from the flask and washed with 6M HCl, H₂ O, and acetone. Theresulting polymer was dried under high vacuum overnight to yield 800 mgpolypropylene. GPC (dichloromethane, polystyrene reference): M_(n)=84,000; M_(w) =96,000; M_(w) /M_(n) =1.14

Example 370

Propylene (100 kPa, absolute) was added to a Schlenk flask charged witha suspension of (2,6-i-PrPh)₂ DABAn!NiBr₂ (12 mg, 1.7×10⁻⁵ mol) in 50 mLof dry toluene. After cooling the mixture to -15° C. in a dry iceisopropanol bath, a 7% MMAO solution in heptane was added. Afterstirring the reaction for 30 min, 5 mL of dry 1-hexene was added and thepropylene removed in vacuo. The polymerization was allowed to stir foran additional 30 min before acetoneand water were added to quench thepolymerization and precipitate the polymer. Solidpolypropylene-b-poly(1-hexene) was recovered from the flaskand washedwith 6M HCl, H₂ O, and acetone. The resulting polymer was dried underhigh vacuum overnight to yield 1.8 g polypropylene-b-poly(1-hexene). GPC(dichloromethane, polystyrene reference): M_(n) =142,000; M_(w)=165,000; M_(w) /M_(n) =1.16. ¹ H-NMR analysis: indicates the presenceof both a polypropylene and poly(1-hexene) block. ¹ H-NMR also suggeststhat the DP of the propylene block is substantially higher than the DPof the 1-hexene block.DSC analysis: T_(g) =-18° C. corresponding to thepolypropylene block. No other transitions were observed.

Example 371

1-Octadecene (4 mL, 8 vol %) was added to a suspension of (2,6-i-PrPh)₂DABAn!NiBr₂ (12 mg, 1.6×10⁻⁵ mol) in 50 mL of dry toluene. The flask wascooled to -10° C. in a dry ice isopropanol bath and 2 mL of a 7% MMAOsolution in heptane was added. After stirring the reaction for 1 h,acetone and water were added to quench the polymerization andprecipitate the polymer. Solid poly(1-octadecene) was recovered from theflask collected and washed with 6M HCl, H₂ O, and acetone. The resultingpolymer was dried under highvacuum overnight to yield 200 mgpoly(1-octadecene). GPC (trichlorobenzene,135° C., polystyrenereference): M_(n) =19,300; M_(w) =22,700; M_(w) /M_(n) =1.16. DSC: T_(m)=37° C. ¹ H-NMR (CDCl₃) analysis 47 branches/1000 C (theoretical 56branches/1000 C).

Example 372

A 12-mg (0.022 mmol) sample of (para-Me--Ph)₂ DABMe₂ !NiBr₂was placed ina Parr® 1000 mL stirred autoclave under an argon atmosphere with 200 mLof dry toluene (reactor temperature was 65° C.). The reactor was purgedwith ethylene and 1.5 mL (100 eq) of a 10% MAOsolution in toluene wasadded to the suspension. The autoclave was rapidly pressurized to 5.5MPa and the reaction was stirred for 60 min. A 15° C. exotherm wasobserved. The oligomerization was quenched uponaddition of acetone andwater. The solvent was removed in vacuo resulting in 20 g of ethyleneoligomers. ¹ H-NMR (CDCl₃) analysis 83% α-olefin.

Example 373

A 12-mg (0.022 mmol) sample of Ph₂ DABAn!NiBr₂ was placed in a Parr®1000 mL stirred autoclave under an argon atmosphere with 200 mL of drytoluene (reactor temperature was 55° C.). The reactor was purged withethylene and 2 mL (100 eq) of a 7% MMAO solution in heptane was added tothe suspension. The autoclave was rapidly pressurized to 5.5 MPa and thereaction was stirred for 60 minutes. A 18° C. exotherm was observed. Theoligomerization was quenched upon addition of acetone and water. Thesolvent was removed in vacuo resulting in 26 g (corrected for loss ofC₄, C₆, and C₈ during work-up) of ethylene oligomers. ¹ H-NMR (CDCl₃)and GC analysis: Distribution: C₄ -C₁₈, C₄ =6.0%, C₆ =21%, C₈ =22%, C₁₀=17%, C₁₂ =16%, C₁₄ =13%, C₁₆ =5%, C₁₈ =trace; 90% α-olefin.

Example 374

A 12-mg (0.022 mmol) sample of Ph₂ DABAn!NiBr₂ was placed in a Parr®1000 mL stirred autoclave under an argon atmosphere with 200 mL of drytoluene (reactor temperature was 45° C.). The reactor was purged withethylene and 2 mL (100 eq) of a 7% MMAO solution in heptane was added tothe suspension. The autoclave was rapidly pressurized to 5.5 MPa and thereaction was stirred for 60 min. The oligomerization was quenched uponaddition of acetone and water. The solvent was removed in vacuoresulting in 32 g (corrected for loss of C₄, C₆, and C₈ during work-up)of ethylene oligomers. ¹ H-NMR (CDCl₃) and GC analysis: Distribution: C₄-C₂₀, C₄ =9.0%, C₆ =19%, C₈ =19%, C₁₀ =15%, C₁₂ =14%, C₁₄ =11%, C₁₆ =5%,C₁₈ =4%, C₂₀ =2%; 92% α-olefin.

Example 375

A 12-mg (0.022 mmol) sample of (Ph)DABAn!NiBr₂ was placed in a 1000 mLstirred autoclave under an argon atmosphere with 200 mL of deaeratedtoluene (reactor temperature was 25° C.). The reactor was purged withethylene and 2 mL (100 eq) of a 10% MAO solution in toluene was addedtothe suspension. The autoclave was rapidly pressurized to 2.1 MPa andthereaction was stirred for 30 min. A 20° C. exotherm was observed.Theoligomerization was quenched upon addition of acetone and water. Thesolvent was removed in vacuo resulting in 16.1 g of a fluid/waxy mixture(50,000 TO/h based on isolated oligomer). ¹ H-NMR (CDCl₃) analysis 80%α-olefin. Distribution of isolated oligomers by GC analysis: C₁₀ =20%,C₁₂ =28%, C₁₄ =23%, C₁₆ 15%, C₁₈ 32 10%, C₂₀ =4%. All C₄, C₆, C₈ andsome C₁₀ was lost during work-up.

Example 376

A 12-mg (0.022 mmol) sample of (Ph)DABAn!NiBr₂ was placed in a 1000 mLstirred autoclave under an argon atmosphere with 200 mL of deaeratedtoluene (reactor temperature was 25° C.). The reactor was purged withethylene and 2 mL (100 eq) of a 10% MAO solution in toluene was addedtothe suspension. The autoclave was rapidly pressurized to 4.1 MPa andthereaction was stirred for 60 minutes. A 20° C. exotherm wasobserved.The oligomerization was quenched upon addition of acetone andwater. The solvent was removed in vacuo resulting in 28.3 g of crudeproduct (50,000 TO/h based on isolated oligomer). Trace Al was removedby an aqueous/organic work-up of the crude mixture. ¹ H-NMR (CDCl₃)analysis 85% α-olefin. Distribution of isolated oligomers by GCanalysis: C₁₀ =13%, C₁₂ =30%, C₁₄ =26%, C₁₆ =18%, C₁₀ =10%, C₂₀ =3%. AllC₄, C₆, C₈ and some C₁₀ was lost during work-up.

Example 377

A 12-mg (0.022 mmol) sample of (Ph)DABAn!NiBr₂ was placed in a 1000 mLstirred autoclave under an argon atmosphere with 200 mL of deaeratedtoluene (reactor temperature was 25° C.). The reactor was purged withethylene and 2 mL (100 eq) of a 10% MAO solution in toluene was addedtothe suspension. The autoclave was rapidly pressurized to 6.7 MPa andthereaction was stirred for 60 min. A 15° C. exotherm was observed.Theoligomerization was quenched upon addition of acetone and water. Thesolvent was removed in vacuo resulting in 21.6 g of crude product(40,000 TO/h based on isolated oligomer). ¹ H-NMR (CDCl₃) analysis 93%α-olefin. Distribution of isolated oligomers by GC analysis: C₁₀ =13%,C₁₂ =27%, C₁₄ =26%, C₁₆ =18%, C₁₈ =12%,C₂₀ =5%. All C₄, C₆, C₈ and someC₁₀ was lost during work-up.

Example 378

A 12-mg (0.022 mmol) sample of Ph₂ DABAn!NiBr₂ was placed in a 1000 mLstirred autoclave under an argon atmosphere with 200 mL of dry toluene(reactor temperature was 50° C.). The reactor was purged with ethyleneand 2 mL (100 eq) of a 10% MAO solution in toluene was addedto thesuspension. The autoclave was rapidly pressurized to 5.5 MPa andthereaction was stirred for 60 minutes. A 15° C. exotherm wasobserved.The oligomerization was quenched upon addition of acetone andwater. The solvent was removed in vacuo resulting in 22.3 g of crudeproduct (40,000 TO/h based on isolated oligomer). ¹ H-NMR (CDCl₃)analysis 92% α-olefin. Distribution of isolated oligomers by GCanalysis: C₁₀ =10%, C₁₂ =28%, C₁₄ =25%, C₁₆ =19%, C₁₈ =12%,C₂₀ =6%. AllC₄, C₆, C₈ and some C₁₀ was lost during work-up.

Examples 379-393 General Procedure for Copolymerizations

(a) Experiments at Ambient Pressure: A Schlenk flask containing thecatalyst precursor was cooled to -78° C., evacuated, and placed under anethylene atmosphere. In subsequent additions, methylene chloride and theacrylate were added to the cold flask via syringe. The solution wasallowed to warm to room temperature and stirred with a magnetic stirbar. After the specified reaction time, the reaction mixture was addedto ˜600 mL of methanol in order to precipitate the polymer. Next, themethanol was decanted off of the polymer, which was then dissolved in˜600 mL of Et₂ O or petroleum ether. (For copolymerizations with FOA, asecond precipitation of the polymer solution into methanol wasoftennecessary in order to remove all of the acrylate from the polymer.) Thesolution was filtered though a plug of Celite® and/or neutral alumina,the solvent was removed, and the polymer was dried in vacuo for severaldays. The copolymers were isolated as clear, free-flowing or viscousoils. The copolymers were often darkened by traces of palladium black,which proved difficult to remove in some cases. Polymers with high FOAincorporation were white, presumably due to phase separation of thefluorinated and hydrocarbon segments.

(b) Experiments at Elevated Pressure: Reactions were carried out in amechanically stirred 300 mL Parr® reactor, equipped with an electricheating mantle controlled by a thermocouple dipping into the reactionmixture. A solution of 0.1 mmol of catalyst precursor in methylenechloride, containing the functionalized comonomer (5-50 mL, total volumeof the liquid phase: 100 mL), was transferred via cannula to the reactorunder a nitrogen atmosphere. After repeatedly flushing with ethylene orpropylene, constant pressure was applied by continuously feeding thegaseous olefin and the contents of the reactor were vigorously stirred.After the specified reaction time, the gas was vented. Volatiles wereremoved from the reaction mixture in vacuo, and the polymer was driedunder vacuum overnight. In representative runs, the volatile fractionwas analyzed by GC for dow-molecular-weight products. Residual monomers(tBuA,FOA) or homooligomers of the functionalized comonomer (MVK) wereremoved byprecipitating the polymer from methylene chloride solutionwith methanol. This procedure did not significantly alter the polymercomposition.

Copolymer Spectral Data. In addition to the signals of the methyl,methylene and methine groups originating from ethylene or propylene, the¹ H and ¹³ C NMR spectra of the copolymers exhibit characteristicresonances due to the functionalized comonomer. The IR-spectra displaythe carbonyl band of the functional groups originating from thecomonomer.

Ethylene-MA Copolymer

¹ H NMR (CDCl₃, 400 MHz) δ3.64 (s, OCH₃), 2.28 (t, J=7, CH₂ C(O)), 1.58(m, CH₂ CH₂ C(O)); ¹³ C NMR (C₆ D₆, 100 MHz) δ176 (C(O)), 50.9 (OCH₃);IR (film):1744 cm⁻¹ ν(C(O))!.

Ethylene-FOA Copolymer

¹ H NMR (CDCl₃, 400 MHz) δ4.58 (t, J_(HF) =14, OCH₂ (CF₂)₆ CF₃), 2.40(t, J=7, CH₂ C(O)), 1.64 (m, CH₂ CH₂ C(O)); ¹³ C NMR (CDCl₃, 100 MHz)δ172.1 (C(O)), 59.3 (t, J_(CF) =27, OCH₂ (CF2)₆ CF₃); IR (film):1767cm⁻¹ ν(C(O))!.

Ethylene-tBuA Copolymer

¹ H NMR (CDCl₃, 300 MHz) δ2.18 (t, J=7, CH₂ C(O)), 1.55 (m, CH₂ CH₂C(O)), 1.42 (s, OCMe₃); ¹³ C NMR (CDCl₃, 62 MHz) δ173.4 (C(O)); IR(film): 1734 cm⁻¹ (CO).

Ethylene-MVK Copolymer

¹ H NMR (CDCl₃, 250 MHz) δ2.39 (t, J=7, CH₂ C(O)), 2.11 (s, C(O)CH₃),1.5 (m, CH₂ CH₂ C(O)); ¹³ C NMR (CDCl₃, 62 MHz) δ209 (C(O)); IR (film):1722 cm⁻¹ ν(C(O))!.

Propylene-MA Copolymer

¹ H NMR (CDCl₃, 250 MHz) δ3.64 (s, OCH₃), 2.3 (m, CH₂ C(O)); ¹³ C NMR(CDCl₃, 62 MHz) δ174.5 (C(O)), 51.4 (OCH₃); IR (film): 1747 cm⁻¹ν(C(O))!.

Propylene-FOA Copolymer

¹ H NMR (CDCl₃, 250 MHz) δ4.57 (t, J_(HF) =14, OCH₂ (CF₂)₆ CF₃), 2.39(m, CH₂ C(O)); ¹³ C NMR (CDCl₃, 62 MHz) δ172.2 (C(O)), 59.3 (t, J_(CF)=27, OCH₂(CF₂)₆ CF₃); IR (film): 1767 cm⁻¹ ν(C(O))!.

Results of the various polymerization are given in the Table below.

    __________________________________________________________________________               react.  results         polymer    Ex.   monomers               conc.   mass                           comon.                               TON.sup.e                                       M.sub.n.sup.f    Ex.       cat..sup.b          c    comon.                   p (atm)                       polymer                           incorp..sup.d                               E re. P                                   Comon.                                       (× 10.sup.-3)                                           M/M    __________________________________________________________________________    379       6b E/MA 0.6 M                   2   22.2                           1.0%                               7710                                   78  88  1.8    380       6b E/MA 2.9 M                   2   4.3 6.1%                               1296                                   84  26  1.6    381       6b E/MA 5.8 M                   2   1.8 12.1%                               455 63  11  1.6    382       6b E/MA 5.8 M                   6   11.2                           4.0%                               3560                                   148 42  1.8    383       6a E/MA 5.8 M                   6   1.2 5.0%                               355 19  0.3.sup.g                                           --    384       6b E/MA 5.8 M                   6   1.2 4.7%                               364 18  10  1.8    385       6b E/tBuA               3.4 M                   6   2.8 0.7%                               956 7   25  1.6    386       6b E/tBuA               0.4 M                   1   1.9 0.4%                               665 3   6   1.8    387       1a E/FOA               0.6 M                   1   1.5 0.3%                               506 2   3   1.6    388       1b E/FOA               0.6 M                   1   27.5                           0.6%                               8928                                   55  106 3.1    389       6b E/FOA               1.8 1   9.5 0.9%                               2962                                   27  95  2.7    390       6b E/MVK               3.0 M                   6   1.8 1.3%                               626 8   7   1.5    391       6b E    --  6   10.3                           --  37127   384 3.1    392       6b P/MA 0.6 M                   6   5.0 1.1%                               1179                                   13  37  1.8    393       6b P/FOA               1.8 M                   2   1.0 5.6%                               145 9   18  1.8    __________________________________________________________________________     .sup.a 0.1 mmol catalyst (Ex. 391: 0.01 mmol); solvent: CH.sub.2 Cl.sub.2     (total volume CH.sub.2 Cl.sub.2 and comonomer: 100 mL; Ex. 387 & 388: 60     mL) temperature: 35° C. (Ex. 386-389 & 391° C.); reaction     time: 18.5 h (Ex. 386-388: 24 h; Ex. 389, 37 h);     .sup.b Complexes 6: { (2,6i-PrPh).sub.2 DABR.sub.2 !Pd CH.sub.2 CH.sub.2     CH.sub.2 C(O)OMe!}BAF (6a); R = Me (6b); Complexes 1: { (2,6i-PrPh).sub.2     DABR.sub.2 ! Pd(Me) (OEt.sub.2) BAF; R = H (1a); R = Me (1b));     .sup.c Ethylene (E), propylene (P), methyl acrylate (MA), tertbutyl     acrylate (tBuA), H.sub.2 C═CHC(O)OCH.sub.2 (CF.sub.2).sub.6 CF.sub.3     (FOA), methyl vinyl ketone (MVK).     .sup.d In mol %.     .sup.e Turnover number = moles of substrate converted per mole of     catalyst.     .sup.f Determined by GPC vs. polystyrene standards;     .sup.g determined by .sup.1 H NMR spectroscopy of the nonvolatile product     fraction; ˜0.5 g of volatile products formed additionally;     .sup.h Branching: Ethylene Copolymers: ˜100 methyl groups/1000     carbon atoms (Tg's ˜-77--67° C.); Propylene Copolymers: -210     methyl groups/1000 carbon atoms.

Example 394

Et₂ O (30 mL) was added to a round bottom flask containing 445 mg (1.10mmol) of (2,6-i-PrPh)₂ DABMe₂ and 316 mg (1.15 mmol) of Ni(COD)₂. Methylacrylate (100 μL) was then added to the flask viamicroliter syringe. Theresulting blue solution was stirred for several hours before the Et₂ Owas removed in vacuo. The compound was then dissolved in petroleum etherand the resulting solution was filtered and then cooled to -35° C. inthe drybox freezer. Purple single crystals of (2,6-i-PrPh)₂ DABMe₂ !NiH₂ C═CHCO(OMe)! were isolated: ¹ H NMR (CD₂ Cl₂, 300 MHz, -40° C.)δ7.4-7.2 (m, 6, H_(aryl)), 3.74 (br septet, 1, CHMe₂), 3.09 (septet, 1,J=6.75, C'HMe₂), 2.93 (septet, 1, J=6.75, C"HMe₂), 2.85 (s, 3, OMe),2.37 (br septet, 1, C'"HMe₂), 2.10 (dd, 1, J=13.49,8.10, H₂C═CHC(O)OMe), 1.66 (dd, 1, J=13.49, 4.05, HH'C═CHC(O)OMe), 1.41 (d, 3,J=6.75, CHMeMe'), 1.35 (dd, 1, J=8.10, 4.05, HH'C═CHC(O)OMe), 1.26 (d,3, J=8.10, C"HMeMe'), 1.24 (d, 3, J=8.09, C'HMeMe'), 1.13 (d, 3, J=6.75,C'HMeMe'), 1.09-1.03 (doublets, 12,CHMeMe', C"HMeMe', C'"HMeMe'), 0.79and 0.62 (s, 3 each, N═C(Me)--C'(Me)═N); ¹³ C NMR (CD₂ Cl₂, 300 MHz,-20° C.) δ174.2 (C(O)OMe), 166.6 and 165.5 (N═C--C'═N), 147.9 and 146.8(Ar, Ar': C_(ipso)), 139.5, 139.0, 138.2 and 137.7 (Ar: C_(o), C'_(o)and Ar': C_(o), C'_(o)), 125.6 and 125.4 (Ar, Ar': C_(p)), 123.5, 123.4,123.3 and 123.0 (Ar: C_(m), C'_(m) and Ar': C_(m), C'_(m)), 49.9 and39.8 (H₂ C═CHC(O)OMe), 28.8, 28.5, 28.4 and 28.3 (CHMe₂, C'HMe₂, C"HMe₂,C'"HMe₂), 26.1 (H₂ C═CHC(O)OMe), 24.3, 23.8, 23.6, 23.4, 23.0, 22.9,22.7 and 22.7 (CHMeMe', C'HMeMe', C"HMeMe', C'"HMeMe'), 20.21 and 20.16(N═C(Me)--C'(Me)═N).

Example 395

In a nitrogen-filled drybox, 289 mg (0.525 mmol) of (2,6-i-PrPh)₂ DABMe₂Ni(H₂ C═CHCO(OMe))! and 532 mg (0.525 mmol) of H(OEt₂)₂ BAF were placedtogether in a round bottom flask. The flask was cooled in the -35° C.freezer before adding 20 mL of cold(-35° C.) Et₂ O to it. The reactionmixture was then allowed towarm to room temperature as it was stirredfor 2 h. The solution was then filtered and the solvent was removed invacuo to yield 594 mg (80.1%) of the 4-membered chelate, { (2,6-i-PrPh)₂DABMe₂ !Ni CHMeC(O)OMe!}BAF, as a burnt orange powder: ¹ H NMR (CD₂ Cl₂,300 MHz, rt) δ7.72 (s, 8, BAF: H_(o)), 7.56 (s, 4, BAF: H_(p)), 7.5-7.2(m, 6, H_(aryl)), 3.52 (s, 3, OMe), 3.21 (q, 1, J=6.75, CHMeC(O)OMe),3.45, 3.24, 3.02 and 3.02 (septet, 1 each, CHMe₂, C'HMe₂, C"HMe₂ andC'"HMe₂), 2.11 and 2.00 (s, 3 each, N═C(Me)--C'(Me)═N), 1.55, 1.50,1.47, 1.33, 1.28, 1.24, 1.23 and 1.17 (d, 3 each, CHMeMe', C'HMeMe',C"HMeMe' and C'"HMeMe'), -0.63 (d, 3, J=6.75, CHMeC(O)OMe); ¹³ C NMR(CD₂ Cl₂, 300 MHz, rt) δ178.2, 177.0 and 174.1 (C(O)OMe, N═C--C'═N),162.2(q, J_(CB) =49.7, BAF: C_(ipso)), 141.2 and 139.8 (Ar, Ar':C_(ipso)), 139.4, 138.89, 138.79 and 138.40 (Ar, Ar': C_(o), C_(o) '),135.2 (BAF: C_(o)), 130.0 and 129.6 (Ar, Ar': C_(p), C_(p) '), 129.3 (q,BAF: C_(m)), 125.6, 125.2, 125.0 and 124.7 (Ar, Ar': C_(m), C'_(m)),125.0 (q, J_(CF) =272.5, BAF: CF₃), 117.9 (BAF: C_(p)), 53.6 (OMe),30.3, 30.0, 29.9 and 29.8 (CHMe₂, C'HMe₂, C"HMe₂, C'"HMe₂), 24.5, 24.1,24.0, 23.7, 23.33, 23.26, 23.1 and23.1 (CHMeMe', C'HMeMe', C"HMeMe',C""HMeMe'), 20.6 and 19.5 (N═C--C'═N), 6.9 (CHMeC(O)OMe).

Examples 396-400

Polymerization of ethylene by { (2,6-i-PrPh)₂ DABMe₂ !NiCHMeC(O)OMe!}BAF. This compound was used to catalyze the polymerizationof polyethylene at temperatures between RT to 80° C.Addition of a Lewisacid often resulted in improved yields of polymer.

General Polymerization Procedure for Examples 396-400

In the drybox, a glass insert was loaded with { (2,6-i-PrPh)₂ DABMe₂ !NiCHMeC(O)OMe!}BAF. In addition, 2 equiv of a Lewis acid (when used) wasadded to the insert. The insert was cooled to -35° C. in a dryboxfreezer, 5 mL of deuterated solvent was added to the cold insert, andthe insert was then capped and sealed. Outside of the drybox, the coldtube was placed under 6.9 MPa of ethylene and allowed to warm to RT or80° C. as it was shaken mechanically for 18 h. An aliquot of thesolution was used to acquire a ¹ H NMR spectrum. The remaining portionwas added to ˜20 mL of MeOH in order to precipitate the polymer. Thepolyethylene was isolated and dried under vacuum.

Example 396

Polymerization Conditions: { (2,6-i-PrPh)₂ DABMe₂ !Ni CHMeC(O)OMe!}BAF(84.8 mg, 0.06 mmol); No Lewis Acid; C₆ D₆ ; RT. No polymer was isolatedand polymer formation was not observed in the ¹ H NMR spectrum.

Example 397

Polymerization Conditions: { (2,6-i-PrPh)₂ DABMe₂ !Ni CHMeC(O)OMe!}BAF(84.8 mg, 0.06 mmol); 2 Equiv BPh₃ ; C₆ D₆, RT. Solid white polyethylene(0.91 g) was isolated.

Example 398

Polymerization Conditions: { (2,6-i-PrPh)₂ DABMe₂ !Ni CHMeC(O)OMe!}BAF(84.8 mg, 0.06 mmol); 2 Equiv B 3,5-trifluoromethylphenyl!₃ ; C₆ D₆, RT.Solid white polyethylene (0.89 g) was isolated.

Example 399

Polymerization Conditions: { (2,6-i-PrPh)₂ DABMe₂ !Ni CHMeC(O)OMe!}BAF;2 Equiv BPh₃ ; C₆ D₆, 80° C. Polyethylene (4.3 g) was isolated as aspongy solid.

Example 400

Polymerization Conditions: { (2,6-i-PrPh)₂ DABMe₂ !Ni CHMeC(O)OMe!}BAF(84.8 mg, 0.06 mmol); No Lewis Acid; CDCl₃, 80° C. Polyethylene (2.7 g)was isolated as a spongy solid.

Example 401

An NMR tube was loaded with { (2,6-i-PrPh)₂ DABH₂ !NiMe(OEt₂)}BAF. Thetube was capped with a septum, the septum was wrapped with Parafilm®,and the tube was cooled to -78° C. CD₂ Cl₂ (700 μL) and one equiv ofmethyl acrylate were added to the cold tube in subsequent additions viagastight microliter syringe. The tube was transferred to the cold NMRprobe. Insertion of methyl acrylate and formation of the 4-memberedchelate complex, { (2,6-i-PrPh)₂ DABH₂ !Ni CHEtC(O)OMe!}BAF, wascomplete at -10° C.: ¹ H NMR (CD₂ Cl₂, 400 MHz, -10° C.) δ8.23 and 8.03(s, 1 each, N═C(H)--C'(H)═N), 7.72 (s, 8, BAF: H_(o)), 7.55 (s, 4, BAF:H_(p)), 7.5-7.2 (m, 6, H_(aryl)), 3.69, 3.51, 3.34 and 3.04 (septet, 1each, CHMe₂, C'HMe₂, C"HMe₂ and C'"HMe₂), 3.58 (s, 3, OMe), 1.48, 1.46,1.46, 1.45, 1.30, 1.27, 1.193 and 1.189 (d, 3 each, J=6.5-7.3, CHMeMe',C'HMeMe', C"HMeMe' and C'"HMeMe'), 0.79 and -0.52 (m, 1 each,CH(CHH'CH₃), 0.68(t, 3, J=6.9, CH(CH₂ CH₃), (CHEt signal was notassigned due to overlap with other protons).

Example 402

A solution of the 4-membered chelate complex { (2,6-i-PrPh)₂ DABH₂ !NiCHEtC(O)OMe!}BAF was allowed to stand at RT for 1 day. During this time,conversion to the 6-membered chelate complex, { (2,6-i-PrPh)₂ DABH₂ !NiCH₂ CH₂ CH₂ C(O)OMe!}BAF, was complete: ¹ H NMR (CD₂ Cl₂, 400 MHz, rt)δ8.47 and 8.01 (s, 1 each, N═C(H)--C'(H)═N), 7.72 (s, 8, BAF: H_(o)),7.56 (s, 4, BAF: H_(p)), 7.5-7.0 (m, 6, H_(aryl)), 3.61(s, 3, OMe), 3.45and 3.09 (septet, 2 each, CHMe₂ and C'HMe₂), 2.25 (t, 2, J 7.3, CH₂C(O)), 1.61 (pentet, 2, J=7.3, NiCH₂ CH₂ CH₂), 1.50, 1.50, 1.46, and1.30 (d, 6 each, J=6.8-6.9, CHMeMe', C'HMeMe'), 0.92 (t, 2, J=7.4,NiCH₂).

Examples 403-407

These Examples illustrate the formation of metallacycles of the formulashown on the right side of the equation, and the use of thesemetallacycles as polymerization catalysts. ##STR91##

In the absence of olefin, the ether-stabilized catalyst derivatives wereobserved to decompose in CD₂ Cl₂ solution with loss of methane. For thecatalyst derivative where M═Pd and R═H, methane loss was accompanied byclean and selective formation of the metallacycle resultingfrom C--Hactivation of one of the aryl i-propyl substituents. This metallacyclecould be isolated, although not cleanly, as its instability and highsolubility prevented recrystallization. Also it could be converted toanother metallacycle in which the diethyl ether ligand is replaced by anolefin ligand, especially ethylene.

Example 403

A 700 μL CD₂ Cl₂ solution of { (2,6-i-PrPh)2DABH₂ !PdMe(OEt₂)}BAF (68.4mg) was allowed to stand at room temperature for several hours and thenat -30° C. overnight. Such highly concentrated solutions of theresulting metallacycle wherein R is H and M is Pd were stable for hoursat room temperature, enabling ¹ H and ¹³ C NMR spectra to be acquired: ¹H NMR (CD₂ Cl₂, 400MHz, 41° C.) δ8.17 (s, 2, N═C(H)--C'(H)═N), 7.75 (s,8, BAF: H_(o)), 7.58 (s, 4, BAF: H_(p)), 7.5-7.0 (m, 6, H_(aryl)), 3.48(q, 4, J=6.88, O(CH₂ CH₃)₂), 3.26 (septet, 1, J=6.49, CHMe₂), 3.08(septet, 1, J=6.86, C'HMe₂), 2.94 (septet, 1, J=6.65, C"HMe₂), 2.70 (dd,1, J=6.67, 0.90, CHMeCHH'Pd), 2.43 (dd, 1,J=7.12, 4.28, CHMeCHH'Pd),2.23 (br m, 1, CHMeCH₂ Pd), 1.54 (d, 3, J=6.86, CHMeCH₂ Pd), 1.43 (d, 3,J=6.79, C"HMeMe'), 1.40 (d, 3, J=7.12, CHMeMe'), 1.37 (d, 3, J=6.95,C'HMeMe'), 1.27 (d, 6, J=6.79, C'HMeMe', C"HMeMe'), 1.12 (d, 3, J=6.54,CHMeMe'), 1.23 (br m, 6, O(CH₂ CH₃)₂), 0.21 (CH₄); ¹³ C NMR (CD₂ Cl₂,400 MHz, 41° C.) δ162.5 (J_(CH) =181.5, N═C(H)), 162.3 (q, J_(BC) =49.8,BAF: C_(ipso)), 161.2 (J_(CH) =178.4, N═C'(H)), 145.8 and 144.5 (Ar,Ar': C_(ipso)), 141.6, 140.7,140.3 and 138.8 (Ar, Ar': C_(ipso)), 135.3(BAF: C_(o)), 131.6 and 129.8 (Ar, Ar': C_(p)), 129.4 (q, J_(CF) =29.9,BAF: CF₃), 128.1,127.6, 125.2 and 124.5 (Ar, Ar': C_(o), C_(o) '), 125.1(BAF: CF₃), 118.0 (BAF: C_(p)), 72 (br, O(CH₂ CH₃)₂), 43.2(CHMeCH₂ Pd),40.5 (CHMeCH₂ Pd), 29.5, 29.1 and 28.8 (CHMe₂,C'HMe₂, C"HMe₂), 26.2(br), 25.3, 25.2, 25.1, 24.5 (br), 23.3 and22.1 (CHMeMe', C'HMeMe',C"HMeMe', CHMeCH₂ Pd), 15.5 (br, O(CH₂ CH₃)₂), -14.8 (CH₄).

Example 404

Addition of ethylene to a CD₂ Cl₂ solution of the compound prepared inExample 403 resulted in loss of ether and formation of the correspondingethylene adduct (spectral data: see Example 405.) Warming ofthe ethyleneadduct in the presence of excess ethylene resulted in branchedpolymerformation: 1.3 ppm (CH₂)_(n), 0.9 ppm (CH₃). For the ethylenepolymerization initiated by this metallacycle, rates of initiation weresignificantly slower than rates of propagation.

Example 405

The metallacycle of Example 403 wherein the diethyl ether ligand wasreplaced by an ethylene ligand was stable enough so that NMR spectracouldbe obtained. ¹ H NMR (CD₂ Cl₂, 400 MHz, -61° C.) δ8.25 and 8.23(N═C(H)--C'(H)═N), 7.74 (s, 8, BAF: H_(o)),7.55 (s, 4, BAF: H_(p)),7.55-7.16 (m, 6, H_(aryl)), 4.67 (m, 2, HH'C═CHH'), 4.40 (m, 2,HH'C═CHH'), 2.95 (septet, 1, J=6.30, CHMe₂), 2.80 (septet, 2, J=6.36,C'HMe₂ and C"HMe₂), 2.53 (br m, 1, CHMeCH₂ Pd), 2.43 (d, 1, J=8.16,CHMeCHH'Pd), 1.73 (dd, 1, J=8.16, 2.84, CHMeCHH'Pd), 1.45 and 1.19 (d, 3each, J=6.79-6.40, CHMeMe'), 1.42 (d, 3, J=7.05, CHMeCH₂ Pd), 1.30,1.30, 1.19 and 0.99 (d, 3 each, J=6.40-6.65, C'HMeMe' and C"HMeMe'); ¹³C NMR (CD₂ Cl₂, 400 MHz, -61° C.) δ162.7 (J_(CH) =179.7, N═CH), 162.1(J_(CH) =180.9, N═C'H), 161.6 (q, J_(CB) =49.7, BAF: C_(ipso)), 144.7,141.7, 141.2, 139.2, 137.5 and 137.1 (Ar, Ar': C_(ipso), C_(o), C'_(o)),134.6 (BAF: C_(o)), 131.0 and 129.0 (Ar,Ar': C_(p)), 128.6 (q, BAF:C_(m)), 124.4 (q, J_(CF) =272.5, BAF: CF₃), 124.6 and 124.0 (Ar, Ar':C_(m)), 117.4 (BAF: C_(p)), 92.3 (J_(CH) =162.4, H₂ C═CH₂), 45.1 (CH₂Pd), 41.1 (CHMeCH₂ Pd), 28.9, 28.5 and 28.2 (CHMe₂, C'HMe₂, C"HMe₂),26.1, 25.6, 25.1, 24.9, 24.6, 22.9 and 21.4 (CHMeMe', C'HMeMe',C"HMeMe', CHMeCH₂ Pd).

Example 406

In a nitrogen-filled drybox, 30 mL of THF was added to a flaskcontaining (2,6-i-PrPh)₂ DABAn (1.87 g, 3.72 mmol) and Ni(COD)₂ (1.02 g,3.72 mmol). The resulting purple solution was stirred for several hoursbefore removing the solvent in vacuo. The product was dissolved in aminimum amount of pentane and the resulting solution was filtered andthenplaced in the drybox freezer (-35° C.) to recrystallize. Purplecrystals of (2,6-i-PrPh)₂ DABAn!Ni(COD) were isolated (1.33 g, 53.5%,first crop). ¹ H NMR (CD₂ Cl₂, 300 MHz, rt) δ7.77 (d, 2, J=8.06,H_(aryl)), 7.44 (t, 2, J=7.52, H_(aryl)), 7.33 (d, 2, J=7.70, H_(aryl)),6.89 (t, 2, J=7.70, H_(aryl)), 6.13 (d,2, J=6.13, H_(aryl)), 3.93 (br s,4, COD: --HC═CH--), 3.48 (septet, 4, J=6.87, CHMe₂), 2.54 (br m, 4, COD:--CHH'--), 1.51 (m, 4, COD: --CHH'--), 1.37 (d, 12, J=6.60, CHMeMe'),0.77 (d, 12, J=6.60, CHMeMe'); ¹³ C NMR (CD₂ Cl₂, 75.5 MHz, rt) δ151.7,151.6, 138.5, 137.1, 133.0, 132.1, 128.8, 125.6, 123.8, 123.7, 119.0(C_(aryl)), 88.7 (COD: --HC═CH--), 29.9 (COD: --CH₂ --), 28.0, 25.1 and23.8 (CHMeMe').

Example 407

In the drybox, a glass insert was loaded with 35.2 mg (0.0527 mmol) of(2,6-i-PrPh)₂ DABAn!Ni(COD) and 55.2 mg (0.0545 mmol) of H(OEt₂)₂ BAF.The insert was cooled to -35° C. in the drybox freezer, 5 mL of CDCl₃was added to the cold insert, and the insert was then capped and sealed.Outside of the drybox, the cold tube was placed under 6.9 MPa ofethylene and allowed to warm to rt as it was shaken mechanically for 18h. An aliquot of the solution was used to acquire a ¹ H NMR spectrum.The remaining portion was added to ˜20 mL of MeOH in order toprecipitate the polymer. The polyethylene(6.1 g) was isolated and driedunder vacuum.

Examples 408-412

(acac)NiEt(PPh₃) was synthesized according to published procedures(Cotton, F. A.; Frenz, B. A.; Hunter, D. L. J. Am. Chem. Soc. 1974, 96,4820-4825).

General Polymerization Procedure for Examples 408-412

In the drybox, a glass insert was loaded with 26.9 mg (0.06 mmol) of(acac)NiEt(PPh₃), 53.2 mg (0.06 mmol) of NaBAF, and 0.06 mmol of anα-diimine ligand. In addition, 2 equiv of a phosphine scavenger suchasBPh₃ or CuCl was sometimes added. The insert was cooled to -35° C. inthe drybox freezer, 5 mL of C₆ D₆ was added tothe cold insert, and theinsert was then capped and sealed. Outside of the drybox, the cold tubewas placed under 6.9 MPa of ethylene and allowed to warm to RT as it wasshaken mechanically for 18 h. An aliquot of the solution was used toacquire a ¹ H NMR spectrum. The remaining portion was added to ˜20 mL ofMeOH in order to precipitate the polymer. The polyethylene was isolatedand dried under vacuum.

Example 408

The α-diimine was (2,6-i-PrPh)₂ DABMe₂. Solid white polyethylene (1.6 g)was isolated.

Example 409

The α-diimine was (2,6-i-PrPh)₂ DABMe₂, and 29.1 mg of BPh₃ was alsoadded. Solid white polyethylene (7.5 g) was isolated.

Example 410

The α-diimine was (2,6-i-PrPh)₂ DABMe₂, and 11.9 of CuCl was also added.Solid white polyethylene (0.8 g) was isolated.

Example 411

The α-diimine was (2,6-i-PrPh)₂ DABAn. Solid white polyethylene (0.2 g)was isolated.

Example 412

The α-diimine was (2,6-i-PrPh)₂ DABAn, and 29.1 mg of BPh₃ was alsoadded. Solid white polyethylene (14.7 g) was isolated.

Examples 413-420

The following synthetic methods and polymerization procedures were usedto synthesize and test the polymerization activity of the functionalizedα-diimine ligands of these Examples.

Synthetic Method A

One equiv of glyoxal or the diketone was dissolved in methanol. Twoequiv of the functionalized aniline was added to the solution along with˜1 mL of formic acid. The solution was stirred until a precipitateformed. The precipitate was collected on a frit and washed withmethanol. The product was then dissolved in dichloromethane and theresulting solution was stirred overnight over sodium sulfate. Thesolution was filtered and the solvent was removed in vacuo to yield thefunctionalized α-diimine.

Synthetic Method B

One equiv of glyoxal or the diketone was dissolved in dichloromethaneand two equiv of the functionalized aniline was added to the solution.The reaction mixture was stirred over sodium sulfate (˜1 week). Thesolution was filtered and the solvent was removed in vacuo. The productwas washed or recrystallized from petroleum ether and then dried invacuo.

Nickel Polymerization Procedure

In the drybox, a glass insert was loaded with one equiv each ofNi(COD)₂, H(OEt₂)₂ BAF, and the α-diimine ligand. Theinsert was cooledto -35° C. in the drybox freezer, 5 mL of C₆ D₆ was added to the coldinsert, and the insert was then capped and sealed. Outside of thedrybox, the cold tube was placed under 6.9 MPa of ethylene and allowedto warm to RT as it was shaken mechanically for 18 h.An aliquot of thesolution was used to acquire a ¹ H NMR spectrum. Theremaining portionwas added to ˜20 mL of MeOH in order to precipitatethe polymer. Thepolyethylene was isolated and dried under vacuum.

Palladium Polymerization Procedure

In the drybox, a glass insert was loaded with one equiv each ofCODPdMe(NCMe)!BAF and the α-diimine ligand. The insert was cooled to-35° C. in the drybox freezer, 5 mL of C₆ D₆ was addedto the coldinsert, and the insert was then capped and sealed. Outside of thedrybox, the cold tube was placed under 6.9 MPa of ethylene and allowedtowarm to RT as it was shaken mechanically for 18 h. An aliquot of thesolution was used to acquire a ¹ H NMR spectrum. The remaining portionwas added to ˜20 mL of MeOH in order to precipitate the polymer. Thepolyethylene was isolated and dried under vacuum.

Example 413 α-Diimine was (2-hydroxyethylPh)₂ DABMe₂

Synthetic Method B

¹ H NMR (CDCl₃, 300 MHz, rt) δ7.28-7.20 (m, 4, H_(aryl)),7.12 (t, 2,J=7.52, H_(aryl)), 6.67 (d, 2, J=7.67, H_(aryl)), 3.74 (t, 4, J=6.79,CH₂ OH), 3.11 (br s, 2, OH), 2.76 (t, 4, J=6.79, CH₂ CH₂ OH), 2.16 (s,6, N═C(Me)--C(Me)═N); ¹³ C NMR (CDCl₃, 75 MHz, rt) δ168.2 (N═C--C═N),149.0 (Ar: C_(ipso)), 128.4 (Ar: C_(o)), 130.4, 127.1, 124.6 and 118.2(Ar: C_(m), C_(p), C_(m) ', C_(o) '), 62.9 (CH₂ OH), 35.3 (CH₂ CH₂ OH),15.8 (N═C(Me)--C(Me)═N).

Nickel Polymerization Procedure

(0.02 mmol scale) Seventy mg of polyethylene was isolated. ¹ H NMRspectrum (C₆ D₆) shows the production of 1- and 2-butenes alone withsmaller amounts of higher olefins.

Palladium Polymerization Procedure

(0.06 mmol scale) No polymer was isolated, however, the ¹ H NMR spectrumshows peaks consistent with the formation of branched polyethylene: 1.3ppm (CH₂)_(n), 0.9 ppm (CH₃ of branches). Broad α-olefinic resonancesare observed in the baseline.

Example 414 α-Diimine is (2,6-Et-3,5-chloroPh)₂ DABMe₂

Synthetic Method A

¹ H NMR (CDCl₃, 300 MHz, rt) δ7.19 (s, 1, H_(aryl)), 2.64(sextet, 4,J=7.19, CHH'CH₃), 2.36 (sextet, 4, J=7.11, CHH'CH₃), 2.10 (s, 6,N═C(Me)--C(Me)═N), 1.05 (t, 12, J=7.52, CH₂ CH₃); ¹³ C NMR (CDCl₃, 75MHz, rt) δ168.8 (N═C--C═N), 149.3 (Ar: C_(ipso)), 132.3 and 127.4 (Ar:C_(o) and C_(m)), 124.7 (Ar: C_(p)), 22.5 (CH₂ CH₃), 16.8(N═C(Me)--C(Me)═N), 12.1 (CH₂ CH₃).

Nickel Polymerization Procedure

(0.06 mmol scale) Solid white polyethylene (14.6 g) was isolated.

Palladium Polymerization Procedure

(0.06 mmol scale) Polyethylene (0.06 g) was isolated as an oil. ¹ H NMRspectrum (C₆ D₆) shows branched polyethylene along with someinternalolefinic end groups.

Palladium Polymerization Procedure

{0.03 mmol scale; Isolated (2,6-Et-3,5-chloroph)₂ DABMe₂)!PdMe(NCMe)!BAFwas used.} Polyethylene (2.42 g) was isolated as an oil.

Example 415 α-Diimine is (2,6-Et-3-chloroPh)₂ DABMe₂

Synthetic Method A

¹ H NMR (CDCl₃, 300 MHz, rt) δ7.10 (d, 2, J=8.43, H_(aryl)), 7.04 (d, 2,J=8.07, H_(aryl)), 2.65 (m, 2, CHH'CH₃), 2.49 (m, 2, CHH'CH₃), 2.30 (m,4, C'HH'C'H₃), 2.08 (s, 6, N═C(Me)--C(Me)═N), 1.15 and 1.07 (t, 6 each,J=7.52, CH₂ CH₃ and C'H₂ C'H₃); ¹³ C NMR (CDCl₃, 75 MHz, rt) δ168.4(N═C--C═N), 148.5 (Ar: C_(ipso)), 132.0, 129.1 and 128.6 (Ar: C_(o),C_(o) ', C_(m)), 126.9 and 124.3 (Ar: C_(m) ' and C_(p)), 24.4 and 22.6(CH₂ CH₃ and C'H₂ C'H₃), 16.5 (N═C(Me)--C(Me)═N), 13.4 and 12.4 (CH₂ CH₃and C'H₂ C'H₃).

Palladium Polymerization Procedure

{0.03 mmol scale; Isolated (2,6-Et-3-chloroPh)₂ DABMe₂)Pdme(NCMe)!BAFwas used.} Polyethylene (˜1 g) was isolated as an amorphous solid.

Example 416 α-Diimine is (2,6-bromo-4-MePh)₂ DABMe₂

Synthetic Method A

¹ H NMR (CDCl₃, 300 MHz, rt) δ7.40 (m, 4, H_(aryl)), 2.32(s, 6, Ar: Me),2.14 (s, 6, N═C(Me)--C(Me)═N); ¹³ C NMR (CDCl₃, 75 MHz, rt) δ171.5(N═C--C═N), 144.9 (Ar: C_(ipso)), 135.7 (Ar: C_(p)), 132.4 (Ar: C_(m)),112.3 (Ar: C_(o)), 20.2 and 16.9 (N═C(Me)--C(Me)═N and Ar: Me)

Nickel Polymerization Procedure

(0.02 mmol scale) Solid white polyethylene (5.9 g) was isolated. ¹ H NMRspectrum (C₆ D₆) shows a significant amount of branched polymer alongwith internal olefinic end groups.

Palladium Polymerization Procedure

(0.06 mmol scale) Polyethylene (0.38 g) was isolated as an oil. ¹ H NMRspectrum (C₆ D₆) shows a significant amount of branched polymer alongwith internal olefinic end groups.

Example 417 α-Diimine is (2,6-Me-4-bromoPh)₂ DABH₂

Synthetic Method A

¹ H NMR (CDCl₃, 300 MHz, rt) δ8.07 (s, 2, N═CH--CH═N), 7.24 (s, 4,H_(aryl)), 2.15 (s, 12, Ar: Me); ¹³ C NMR (CDCl₃, 300 MHz, rt) δ163.6(N═C--C═N), 148.7 (Ar: C_(ipso)), 131.0 and 128.7 (Ar: C_(o) and C_(m)),117.7 (Ar: C_(p)), 18.1 (Ar: Me).

Nickel Polymerization Procedure

(0.06 mmol scale) Solid white polyethylene (9.5 g) was isolated.

Palladium Polymerization Procedure

(0.06 mmol scale) No polymer was isolated, however, the ¹ H NMR spectrum(C₆ D₆) shows the production of α- and internal olefins (butenes andhigher olefins). A small resonance exists at 1.3 ppm and is consistentwith the resonance for (CH₂)_(n).

Example 418 α-Diimine is (2,6-Me-4-bromoPh)₂ DABMe₂

Synthetic Method A

¹ H NMR (CDCl₃, 300 MHz, rt) δ7.22 (s, 4, H_(aryl)), 2.02(s, 6,N═C(Me)--C(Me)═N), 2.00 (s, 12, Ar: Me); ¹³ C NMR (CDCl₃, 75 MHz, rt)δ168.5 (N═C--C═N), 147.3 (Ar: C_(ipso)), 130.6 (Ar: C_(m)), 126.9 (Ar:C_(o)), 115.9 (Ar: C_(p)), 17.6 (Ar: Me), 15.9 (N═C(Me)--C(Me)═N).

Nickel Polymerization Procedure

(0.06 mmol scale) Solid white polyethylene (14.9 g) was isolated.

Palladium Polymerization Procedure

(0.06 mmol scale) Polyethylene (1.3 g) was isolated as an oil. The ¹HNMR spectrum (C₆ D₆) shows resonances consistent with the formation ofbranched polymer. Resonances consistent with olefinic end groups areobserved in the baseline.

Palladium Polymerization Procedure

{0.03 mmol scale; Isolated (2,6-Me-4-bromoPh)₂ DABMe₂)PdMe(NCMe)!BAF wasused.} Polyethylene (3.97 g) was isolated as a mixture of a soft whitesolid and an amorphous oil. ¹ H NMR spectrum (C₆ D₆) shows branchedpolyethylene.

Example 419 α-Diimine is (2-Me-6-chloroPh)₂ DABMe₂

Nickel Polymerization Procedure

(0.02 mmol scale) Solid white polyethylene (220 mg) was isolated. Inaddition, the ¹ H NMR spectrum (C₆ D₆) shows the productionof 1- and2-butenes.

Palladium Polymerization Procedure

(0.03 mmol scale; Isolated (2-Me-6-chloroPh)₂ DABMe₂ !PdMe(NCMe)!SbF₆was used.) Polyethylene (3.39 g) was isolated as an oil; The ¹ H NMRspectrum (C₆ D₆) shows the production of branched polyethylene; internalolefin end groups are also present.

Example 420 (2,6-t-BuPh)₂ DABAN

This compound was made by a procedure similar to that of Example 25. Twog (9.74 mmol) of 2,5-di-t-butylaniline and 0.88 g (4.8 mmol) ofacenaphthenequinone were partially dissolved in 50 mL of methanol.Attempted crystallization from ether and from CH₂ Cl₂ yieldedanorange/yellow powder (1.75 g, 66%--not optimized). ¹ H NMR (CDCl₃, 250MHz) δ7.85 (d, 2H, J=8.1 Hz, BIAN: H_(p)), 7.44 (d, 2H, J=8.4 Hz, Ar:H_(m)), 7.33 (dd, 2H, J=8.4, 7.3 Hz, BIAN: H_(m)), 7.20 (dd, 2H, J=8.1,2.2 Hz, Ar: H_(p)), 6.99 (d, 2H, J=2.2 Hz, Ar: H_(o)), 6.86 (d, 2H,J=7.0 Hz, BIAN: H_(o)), 1.37, 1.27 (s, 18H each, C(CH₃)₃).

Example 421

A 100 mg sample of { (2,6-i-PrPh)₂ DAEMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺BAF⁻ in a Schlenk flask was dissolved in CH₂ Cl₂ (4 ml) and cyclopentene(8 ml) added. The flask was flushed well with a 10% ethylene in N₂ mixand the solution stirred with a slow flow of the gas mixture passingthrough the flask. After 15 hours the product had solidified into asingle mass of yellow/brown polymer. The reaction was quenched with MeOHand the polymer broken into pieces and washed with MeOH. Yield=2.0 g.DSC: Tm=165° C. (32 J/g).Integration of the ¹ H-NMR spectrum indicated83 mole % cyclopentene.

Example 422

A 37 mg sample of (2,4,6-MePh)₂ DABAn!NiBr₂ in cyclopentene (5 ml) wasplaced in a Schlenk flask under an atmosphere of ethylene. Modified MAO(1.1 ml, 7.2 wt % Al) was added and the reaction allowed to run for 16hours after which time the product had solidified into a mass of greenpolymer. The reaction was quenched by addition of MeOH/10% HCl and thepolymer was crushed and washed well with MeOH and finally a 2%Irganox/acetone solution. Yield=3.6 g.

Example 423

A 30 mg sample of (2,6-i-PrPh)₂ DABMe₂ !NiBr₂ was slurried in toluene (2ml) and norbornene (2 g). PMAO (1 ml, 9.6 wt % Al) was added. Thesolution immediately turned deep blue/black and in less than a minutebecame extremely viscous. The reaction was quenched after 15 hours byaddition of MeOH/10% HCl causing the polymer to precipitate. The solidwas filtered, washed well with MeOH and finally with a 2% Irganox® 1010in acetone solution. The polymer was cut into pieces and dried.Yield=0.8 g (40%). ¹ H-NMR (ODCB, 120° C.): 1.0-2.5 ppm complexmultiplet confirms that the product is an addition polymer. The absenceof olefinic peaks precludes the existence of ROMP product and indicatesthat the polymer is not of extremely low molecular weight.

Example 424

A 32 mg sample of (2,6-i-PrPh)₂ DABMe₂ !CoCl₂ was slurried in toluene (2ml) and norbornene (4 g). PMAO (1.5 ml, 9.6 wt % Al) was added. Thesolution immediately turned deep purple and within a few minutes becameextremely viscous and difficult to stir. The reaction was quenched after4 hours by addition of MeOH/10% HCl causing the polymer to precipitate.The solid was filtered, washed well with MeOH and finally with a 2%Irganox in acetone solution. The polymer was dried overnight at 110° C.under vacuum. Yield=2.1 g (53%). It was possible to furtherpurify theproduct by dissolving in cyclohexane and reprecipitating with MeOH. ¹H-NMR (TCE, 120° C.): 1.0-2.5 ppm complex multiplet.

Example 425

A 33 mg sample of ((2,4,6-MePh)₂ DABAn)CoCl₂ was slurried in toluene (2ml) and norbornene (4 g). PMAO (2.0 ml, 9.6 wt % Al) was added.Thesolution immediately turned deep blue and within a few minutes theviscosity began to increase. The reaction was quenched after 4 hours byaddition of MeOH/10% HCl causing the polymer to precipitate. The solidwasfiltered, washed well with MeOH and finally with a 2% Irganox® 1010in acetone solution. The polymer was dried overnight at 110° C. undervacuum. Yield=0.8 g (13%). It was possible to further purify the productby dissolving in cyclohexane and reprecipitating with MeOH. ¹ H-NMR(TCE, 120° C.): 1.0-2.5 ppm complex multiplet.

Example 426

A 23 mg sample of (2,4,6-MePh)₂ DABH₂ !PdMeCl was slurried in toluene (2ml) and norbornene (2.7 g). PMAO (1.0 mL, 9.6 wt % Al) was added. Solidsimmediately formed and after a few seconds stirring stopped.The reactionwas quenched after 2 hours by addition of MeOH/10% HCl. The solid wasfiltered, crushed and washed well with MeOH and finally with a 2%Irganox® 1010 in acetone solution. Yield=2.5 g (92%).

Example 427

A 16 mg sample of (2,4,6-MePh)₂ DABH₂ !NiBr₂ was slurried indicyclopentadiene (˜3 g). MMAO (1.2 ml, 7.2 wt % Al) was added. Solutionimmediately turned deep red/purple and started to foam. The reaction wasquenched after 16 hours by addition of MeOH/10% HCl which precipitatedthe polymer. The solid was filtered and washed well with MeOHand finallywith a 2% Irganox® 1010 in acetone solution. Yield=0.25 g.

Example 428

A 20 mg sample of (2,4,6-MePh)₂ DABH₂ !PdMeCl was slurried in toluene (2ml) and ethylidene norbornene (2 ml). PMAO (1.0 mL, 9.6wt % Al)wasadded. The solution turned a pale orange and after an hour the viscosityhad increased. After 14 hours the mixture had solidified into a gel andstirring had stopped. The reaction was quenched by addition of MeOH/10%HCl. The solid was filtered, crushed and washed well with MeOH andfinally with a 2% Irganox® 1010 in acetone solution. Yield=0.7 g (39%).

Example 429

NiI₂ (0.26 g) was placed in THF (10 ml) and (2,6-i-PrPh)₂ DABMe₂ (340mg) was added. The resulting mixture was stirred for 2 days after whichthe THF was removed and pentane added. The red/brown solid was isolatedby filtration and washed several times with pentane. Yield=0.53 g (89%).

A portion of the product (9 mg) in toluene (25 mL) in a Schlenk flaskwas placed under an atmosphere of ethylene (140 kPa absolute!) and 0.25ml PMAO solution (9.6% Al) was added. The solution turned dark greenand, after several hours at room temperature, became viscous. After 16hours the reaction was quenched with MeOH/10% HCl which precipitated thepolymer. The polymer (1.25 g) was collected by filtration, washed wellwith MeOH and dried under reduced pressure. ¹ H NMR indicated ˜133methyl per 1000 methylene.

Example 430

CoI₂ (286 mg) was dissolved in THF (10 ml) and (2,6-iPrPh)₂ DABMe₂ (370mg) was added. The resulting mixture was stirred for 3 days after whichthe THF was removed and pentane added. The brown solid was isolated byfiltration and washed several times with pentane. Yield=0.29 g (44%). ¹H NMR (THF-d₈) 1.0-1.4 (m, 24H, CH--CH₃), 2.06 (s, 6H, N═C--CH₃),2.6-2.8 (m, 4H, C--CH--(CH₃)₂), 7.0-7.3 (m, 6H, aromatic). This data isconsistent with the formula: (2,6-iPrPh)₂ DABMe₂ !CoI₂

A portion of the above product (14 mg, 0.02 mmol) in toluene (25 mL) ina Schlenk flask was placed under an atmosphere of ethylene (140 kPaabsolute!) and 0.4 ml PMAO solution (9.6% Al) was added. The solutionturned purple and, after several hours at room temperature, becameviscous. After 18 hours the reaction was quenched with MeOH/10% HClwhich precipitated the polymer. The polymer (634 mg) was collected byfiltration, washed well with MeOH and dried under reduced pressure. ¹HNMR indicated ˜100 methyl per 1000 methylene. DSC: Tg=-45° C.

Example 431

Solid π-cyclooctenyl-1,5-cyclooctadienecobalt (I) (17 mg, 0.06 mmol)(prepared according to: Gosser L., Inorg. Synth., 17, 112-15, 1977) andsolid (2,6-iPrPh)₂ DABMe₂ (24 mg, 0.06 mmol) were placed in a Schlenkflask and toluene (25 mL) added. An ethylene atmosphere was admitted (34kPa gauge) and the solution stirred for 5 minutes. The final color wasbrown/green. 0.8 ml PMAO solution (9.6% Al) was added. After 18 hoursthe reaction was quenched with MeOH/10% HCl which precipitated thepolymer. The polymer (190 mg) was collected by filtration, washed wellwith MeOH and dried under reduced pressure. ¹ H NMR indicated 90 methylper 1000 methylene. DSC: Tg=-45° C.

Example 432

(2,6-iPrPh)₂ DABMe₂ !CoCl₂ (619 mg) was slurried in Et₂ O (5 ml) andcooled to -25° C. Me₂ Mg (63 mg in 5 ml Et₂ O) was added and thesolution stirred for 15 minutes. Et₂ O was removed under reducedpressure and the resulting bright purple solid was dissolved in pentane,filtered to remove MgCl₂ and the volume reduced to 5 ml. The solutionwas cooled to -25° C. for 2 days and the resulting purple crystalsisolated by filtration. Yield=420 mg (73%). Crystal structuredetermination confirmed that the product was (2,6-iPrPh)₂ DABMe₂ !CoMe₂.

(2,6-iPrPh)₂ DABMe₂ !CoMe₂ (34 mg) in toluene (25 mL) in a Schlenk flaskwas placed under an atmosphere of ethylene (140 kPa absolute!) and afterstirring for 2 hours, 0.6 ml PMAO solution (9.6% Al)was added. Thesolution remained dark purple and, after several hours at roomtemperature, became viscous. After 48 hours the reaction wasquenchedwith MeOH/10% HCl which precipitated the polymer. The polymer(0.838 g) wascollected by filtration, washed well with MeOH and driedunder reduced pressure. Branching (¹ H-NMR): 115 methyl per 1000methylene. DSC: Tg=-45° C.

Example 433

(2,6-iPrPh)₂ DABMe₂ !CoMe₂ (30 mg) was dissolved in benzene(10 ml in ashaker tube) and the solution frozen. Montmorillionite K-10 (AldrichChemical Co., Milwaukee, Wis., U.S.A.)(200 mg, conditioned at 140° C.for 48 hrs under vacuum) suspended in benzene (10 ml) was added on topof the frozen layer and frozen as well. The solution was thawed under anethylene atmosphere (6.9 MPa) and shaken at that pressure for 18 hours.MeOH was added to the resulting polymer which was then isolated byfiltration, washed well with MeOH and dried under reduced pressure.Yield=7.5 g crystalline polyethylene. Branching (¹ H-NMR): 18 Methyl per1000 methylene.

Example 434

(2,6-iPrPh)₂ DABMe₂ !CoMe₂ (15 mg) was dissolved in benzene(10 ml in ashaker tube) and the solution frozen. Montmorillionite K-10 (100 mg,conditioned at 600° C. for 48 hrs under vacuum) suspended in benzene (10ml) was added on top of the frozen layer and frozen as well. Thesolution was thawed under an ethylene atmosphere (6.9 MPa) and shaken atthat pressure for 18 hours. MeOH was added to the resulting polymerwhich was then isolated by filtration, washed well with MeOH and driedunder reduced pressure. Yield=3 g polyethylene. Branching (¹ H NMR): 11Methyl per 1000 methylene.

Example 435

(2,6-iPrPh)₂ DABMe₂ !CoMe₂ (15 mg) was dissolved in benzene(10 ml in ashaker tube) and the solution frozen. Tris(pentaflorophenyl)boron (25mg) dissolved in benzene (10 ml) was addedon top of the frozen layer andfrozen as well. The solution was thawed under an ethylene atmosphere(6.9 MPa) and shaken at that pressure for 18 hours. MeOH was added tothe resulting polymer which was then isolated by filtration, washed wellwith MeOH and dried under reduced pressure. Yield=105 mg polyethylene.Branching (¹ H NMR): 60 Methyl per 1000 methylene.

Example 436

(2,6-iPrPh)₂ DABMe₂ !CoMe₂ (15 mg) was dissolved in benzene(10 ml in ashaker tube) and the solution frozen. HBAF 2Et₂ O (30 mg) slurried inbenzene (10 ml) was added on top of the frozen layer and frozen as well.The solution was thawed under an ethylene atmosphere (6.9 MPa) andshaken at that pressure for 18 hours. MeOH was added to the resultingpolymer which was then isolated by filtration, washed well with MeOH anddried under reduced pressure. Yield=3.8 g polyethylene. Branching(¹ HNMR): 21 Methyl per 1000 methylene.

Example 437

CoCl₂ (102 mg) was placed in acetonitrile and AgBF₄ (306 mg) added. Thesolution was stirred for 30 minutes after which the white AgCl wasfiltered off. (2,6-i-PrPh)₂ DABMe₂ (318 mg) was added and the solutionstirred overnight. The acetonitrile was removed under reducedpressureand pentane added. The orange product was isolated by filtration andwashed and dried. ¹ H-NMR (THF-d₈): 1.1-1.4 (m, C--CH--CH₃, 24H), 1.8(CH₃ CN, 6H), 2.2 (N═C--CH₃, 6H),2.7 (m, C--CH--CH₃, 4H), 7.0-7.2 (m,C═CH, 6H). The spectrum is consistent with the molecular formula:((2,6-iPrPh)₂ DABMe₂)Co(CH₃ CN)₂ !(BF4)₂

A portion of the product (43 mg) in toluene (25 mL) in a Schlenk flaskwas placed under an atmosphere of ethylene (35 kPa gauge) and 0.8 mlPMAO solution (9.6% Al) was added. The solution turned dark purple After18 hours the reaction was quenched with MeOH/10% HCl which precipitatedthe polymer. The polymer (0.310 g) was collected by filtration, washedwell with MeOH and dried under reduced pressure. Branching (¹ H NMR): 72Methyl per 1000 methylene.

Example 438

Solid Co(II) (CH₃)₂ CHC(O)O⁻ !₂ (17 mg, 0.073 mmol) andsolid(2,6-iPrPh)₂ DABMe₂ (32 mg, 0.079 mmol) were placed in a Schlenk flaskand toluene (25 mL) added. An ethylene atmosphere was admitted (140 kPaabsolute!) and 3.0 ml PMAO solution (9.6% Al) was added. After 18 hoursthe reaction was quenched with MeOH/10% HCl which precipitated thepolymer. The polymer (57 mg) was collected by filtration,washed wellwith MeOH and dried under reduced pressure. ¹ H NMR indicated 32 methylper 1000 methylene.

Example 439

The complex { (2,6-EtPh)₂ DABMe₂ !PdMe(NCMe)}⁺ SbF₆.sup. was weighed (50mg, 0.067 mmol) into a 100 mL round-bottom flask inside a dry box.Cyclopentene (20 mL, 3400 equivalents per Pd; unpurified) anddichloromethane (20 mL) were added to the flask, and stirred under anitrogen atmosphere to give a homogeneous solution. A precipitate hadformed after 2 days. After 7 days, the solvent was evaporated and thesolids were dried in a vacuum oven to give 0.39 g polymer (86turnovers/Pd). A sample of the polymer was washed several times withpetroleum ether and ether, then dried in a vacuum oven. The polymer waspressed at 290° C. into a transparent, gray-brown, tough film. DSC (0°to 300° C., 10° C./min, first heat): T_(g) =120° C., T_(m) (onset toend)=179° to 232° C., heat of fusion=18 J/g. ¹ H NMR (400 MHz, 120° C.,ortho-dichlorobenzene-d₄, referenced to solvent peak at 7.280 ppm):0.905 (bs, 1H, cis --CH--CH₂ --CH--), 1.321 (bs, 2H, cis --CH--CH₂ --CH₂--CH--), 1.724 and 1.764 (overlapping bs, 4H, trans --CH--CH₂ --CH₂--CH-- and --CH--CH₂ --CH₂ --CH--), 1.941 (bs, 1H, trans --CH--CH₂--CH--). The ¹ H NMR assignments are based upon 2D NMR correlation ofthe ¹ H and ¹³ C NMR chemical shifts, and are consistent with apoly(cis-1,3-cyclopentylene) repeat unit.

Example 440

The complex { (2,6-iPrPh)₂ DABAn!PdMe(OEt₂)}⁺ SbF₆.sup.was weighed (50mg, 0.054 mmol) into a 100 mL round-bottom flask inside a dry box.Cyclopentene (20 mL, 4200 equivalents per Pd; unpurified) anddichloromethane (20 mL) were added to the flask, and stirred under anitrogen atmosphere to give a homogeneous solution. A precipitate hadformed after 3 days. After 6 days, the solvents were evaporated and thesolids were dried in a vacuum oven to give 0.20 g polymer (55turnovers/Pd). A sample of the polymer was washed several times withpetroleum ether and ether, then dried in a vacuum oven. DSC (0° to 300°C., 10° C./min, first heat): T_(g) =42° C., T_(m) (onset to end)=183° to242° C., heat of fusion=18 J/g. ¹ H NMR (400 MHz, 70° C., CDCl₃,referenced to solvent peak at 7.240 ppm): 0.75 (bm, 1H, cis --CH--CH₂--CH--), 1.20(bs, 2H, cis --CH--CH₂ --CH₂ --CH--), 1.59 and 1.68(overlapping bs, 4H, trans --CH--CH₂ --CH--CH-- and --CH--CH₂ --CH₂--CH--), 1.83 (bs, 1H, trans --CH--CH₂ --CH--). The ¹ H NMR assignmentsare based upon 2D NMR correlation of the ¹ H and ¹³ C NMR chemicalshifts, and are consistent with a poly(cis-1,3-cyclopentylene) repeatunit.

Example 441

The complex (2,6-iPrPh)₂ DABMe₂ !PdMeCl was added (28 mg, 0.050 mmol) toa glass vial containing cyclopentene (3.40 g, 1000 equivalents per Pd;distilled twice from Na) inside a dry box. A solution of MMAO in heptane(1.47 mL, 1.7M Al, 50 equivalents per Pd) was added with stirring togive a homogeneous solution. A precipitate began to form immediately.After 2 days, the solids were collected by vacuum filtration, washedseveral times on the filter with petroleum ether and ether, then driedin a vacuum oven to give 0.254 g polymer (75 turnovers/Pd). The polymerwas pressed at 250° C. into a transparent, gray-brown, tough film. DSC(0° to 300° C., 10° C./min, first heat): T_(g) =114° C., T_(m) (onset toend)=193° to 240° C., heat of fusion=14 J/g. GPC (Dissolved in1,2,4-trichlorobenzene at 150° C., run in tetrachloroethylene at 100°C., polystyrene calibration): peak MW=154,000, M_(n) =70,200, M_(w)=171,000, M_(w) /M_(n) =2.43.

Example 442

The complex { (2,6-iPrPh)₂ DABMe₂ !PdCH₂ CH₂ CH₂ C(O)OCH₃ }⁺ SbF₆.sup.was weighed (42 mg, 0.050 mmol) into a glass vial inside a dry box.Cyclopentene (3.40 g, 1000 equivalents per Pd; distilled twice from Na)and dichloromethane (4.4 mL) were added with stirring to give ahomogeneous solution. After 1 day, the solids were collected by vacuumfiltration, washed several times on the filter with petroleum ether andether, then dried in a vacuum oven to give 1.605 g polymer (471turnovers/Pd). The polymer was pressed at 250° C. intoa transparent,gray-brown, tough film. TGA (25° to 600° C., 10° C./min, nitrogen):T_(d) (onset to end)=473 to 499, 97.06% weight loss. TGA (25° to 600°C., 10° C./min, air): T_(d) =350° C., 5% weight loss. DSC (0° to 300°C.,10° C./min, second heat): T_(g) =94° C., T_(m) (onset to end)=191° to242° C., heat of fusion=14 J/g. GPC (Dissolved in 1,2,4-trichlorobenzeneat 150° C., run in tetrachloroethylene at100° C., polystyrenecalibration): peak MW=152,000, M_(n) =76,000,M_(w) =136,000, M_(w)/M_(n) =1.79.

Example 443

The complex (2,6-iPrPh)₂ DABMe₂ !PdCl₂ was weighed (29 mg, 0.050 mmol)into a glass vial inside a dry box. Cyclopentene was added (6.81 g, 2000equivalents per Pd; distilled from polyphosphoric acid), andthe vial wascooled to <0° C. A solution of MMAO in heptane (1.00 mL, 1.7M Al, 34equivalents per Pd) was added with stirring to give a homogeneoussolution. After 1 day, a copious precipitate had formed. After2 days,the solids were collected by vacuum filtration, washed several times onthe filter with ether and cyclohexane, then dried in a vacuum oven togive 1.774 g polymer (520 turnovers/Pd). The polymer was coated with5000 ppm Irganox® 1010 by evaporating an acetone slurry and drying in avacuum oven. The polymer was pressed at 290° C. into a transparent,gray-brown, tough film. DSC (25° to 330° C., 10° C./min, second heat):T_(g) =105° C., T_(m) (onset to end)=163° to 244° C., heat of fusion=21J/g.

Example 444

The complex (2,6-iPrPh)₂ DABMe₂ !PdCl₂ was weighed (29 mg, 0.050 mmol)into a glass vial inside a dry box. Cyclopentene was added (6.81 g, 2000equivalents per Pd; distilled from polyphosphoric acid), andthe vial wascooled to <0° C. A solution of EtAlCl₂ in hexane (1.7 mL, 1.0M, 34equivalents per Pd) was added with stirring to give a homogeneoussolution. After 4 days, the solids were collected by vacuum filtration,washed several times on the filter with ether and cyclohexane,then driedin a vacuum oven to give 1.427 g polymer (419 turnovers/Pd). Thepolymerwas coated with 5000 ppm Irganox® 1010 by evaporating an acetone slurryand drying in a vacuum oven. The polymer was pressed at 290° C. into atransparent, gray-brown, tough film. DSC (25°to 330° C., 10° C./min,second heat) T_(g) =103° C.,T_(m) (onset to end)=153° to 256° C., heatof fusion=23 J/g.

Example 445

The complex (2,6-iPrPh)₂ DABMe₂ !PdCl₂ was weighed (29 mg, 0.050 mmol)into a glass vial inside a dry box. Cyclopentene was added (6.81 g, 2000equivalents per Pd; distilled from polyphosphoric acid), andthe vial wascooled to <0° C. A solution of EtAlCl₂ aEt₂ AlCl in toluene (1.9 mL,0.91M, 68 equivalents Al per Pd) was added with stirring to give ahomogeneous solution. After 4 days, the solids were collected by vacuumfiltration, washed several times on the filter with ether andcyclohexane, then dried in a vacuum oven to give 1.460 g polymer(429turnovers/Pd). The polymer was coated with 5000 ppm Irganox® 1010 byevaporating an acetone slurry and drying in a vacuum oven. The polymerwas pressed at 290° C. into a transparent, gray-brown, tough film. DSC(25° to 330° C., 10° C./min, second heat): T_(g) =101° C., T_(m) (onsetto end)=161° to 258°C., heat of fusion=22 J/g.

Example 446

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed (32 mg, 0.050 mmol)into a glass vial inside a dry box. Cyclopentene was added (6.81 g, 2000equivalents per Ni; treated with 5 A molecular sieves, and distilledfrom Na and Ph₃ CH), and the vial was cooled to <0° C. A solution ofEtAlCl₂ aEt₂ AlCl in toluene (1.9 mL, 0.91M, 68 equivalents Al per Ni)was added with stirring to give a homogeneous solution. After 5 days,the solids were collected by vacuum filtration, washed several times onthe filter with ether and cyclohexane, and dried in a vacuum oven togive 2.421 g polymer (711 turnovers/Ni). The polymer was coated with5000 ppm Irganox® 1010 by evaporating an acetone slurry and drying in avacuum oven. The polymer was pressed at 290°C. into a transparent,brown, tough film. DSC (25° to 330° C., 10° C./min, second heat) T_(g)=103° C., T_(m) (onset to end)=178° to 272° C., heat of fusion=22 J/g.

Example 447

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed (128 mg, 0.202mmol)into a glass bottle inside a dry box. Cyclopentene was added (27.1g,2000 equivalents per Ni; treated with polyphosphoric acid, anddistilled from Na). A solution of EtAlCl₂ in hexane (6.8 mL, 1.0M, 34equivalents Al per Ni) was added with stirring to give a homogeneoussolution. After 1 day, additional cyclopentene was added (58 g, 6200totalequivalents per Ni) to the bottle containing a heavy slurry. After5 days, the solids were slurried with ether, collected by vacuumfiltration, washed several times with ether and cyclohexane on thefilter, and dried in a vacuum oven to give 36.584 g polymer (2660turnovers/Ni). The polymerwas washed with 50:50 aqueous HCl/MeOH,followed by several washings with 50:50 H₂ O/MeOH, and dried in a vacuumoven. A fine powder sample wasobtained using a 60 mesh screen, andcoated with 5000 ppm Irganox® 1010by evaporating an acetone slurry anddrying in a vacuum oven. The fine powder was pressed at 290° C. into atransparent, pale brown, toughfilm. TGA (25° to 700° C., 10° C./min,nitrogen): T_(d) (onset to end)=478° to 510° C., 99.28% weight loss. DSC(25° to 330° C., 10° C./min, second heat): T_(g) =101° C., T_(m) (onsetto end)=174° to 279°C., heat of fusion=25 J/g. DSC (330° to 25° C., 10°C./min, first cool): T_(c) (onset to end)=247° to 142° C.,heat offusion=28 J/g; T_(c) (peak)=223° C. DSC isothermal crystallizations wereperformed by heating samples to 330° C. followed by rapid cooling to thespecified temperatures, °C., and measuring the exotherm half-times(min): 200 (1.55), 210 (1.57), 220 (1.43), 225 (<1.4), 230 (1.45), 240(1.88), 245 (1.62). DSC thermal fractionation was performed by heating asample to 330° C. followedby stepwise isothermal equilibration at thespecified temperatures, °C., and times (hr): 290 (10), 280 (10), 270(10), 260 (10), 250 (10), 240 (8), 230 (8), 220 (8), 210 (8), 200 (6),190 (6), 180 (6), 170 (6), 160 (4), 150 (4), 140 (4), 130 (3), 120 (3),110 (3). DSC (25°to 330° C., 10° C./min, thermal fractionation sample):T_(g) =100° C.; T_(m), °C. (heat of fusion, J/g)=128 (0.4), 139 (0.8),146 (1.1), 156 (1.5), 166 (1.9), 176 (2.1), 187 (2.6), 197 (3.0), 207(3.2), 216 (3.2), 226 (3.4), 237 (3.6), 248 (3.7), 258 (2.3), 269 (1.2),279 (0.5), 283 (0.1); total heat of fusion=34.6 J/g. DMA(-100° to 200°C., 1, 2, 3, 5, 10 Hz; pressed film): modulus (-100° C.)=2500 MPa, γrelaxation=-67° to -70° C. (activation energy=11 kcal/mol), modulus (25°C.)=1600 MPa, α relaxation (T_(g))=109° to 110° C. (activationenergy=139 kcal/mol).

Example 448

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed (32 mg, 0.050 mmol)into a glass bottle inside a dry box. Cyclopentene was added (34.1 g,10,000 equivalents per Ni; high-purity synthetic material distilled fromNa), and the vial was cooled to <0° C. A solution of MMAO in heptane(2.7 mL, 1.95M Al, 100 equivalents Al per Ni) was added with stirring togive a homogeneous solution. After 3 days, a copious precipitate hadformed. After 7 days, the reaction was quenched with 20 mLMeOH and 2 mLacetylacetone. The solids were collected by vacuum filtration, washedseveral times on the filter with methanol, and dried ina vacuum oven togive 14.365 g polymer (4200 turnovers/Ni). The polymer wascoated with5000 ppm Irganox® 1010 by evaporating an acetone slurry anddrying in avacuum oven. The polymer was pressed at 290° C. into a transparent,colorless, tough film. DSC (0° to 320° C., 20° C./min, second heat):T_(g) =95° C., T_(m) (onset toend)=175° to 287° C., heat of fusion=20J/g.

Example 449

The complex (2,4,6-MePh)₂ DABAn!NiBr₂ was weighed (32 mg, 0.050 mmol)into a glass bottle inside a dry box. Cyclopentene was added (34.1 g,10,000 equivalents per Ni; high-purity synthetic material distilled fromNa), and the vial was cooled to <0° C. A solution of EtAlCl₂ aEt₂ AlClin toluene (2.8 mL, 0.91M, 100 equivalents Al per Ni) was added withstirring to give a homogeneous solution. After 3 days, a precipitate hadformed. After 7 days, the reaction was quenched with 20 mL MeOh and 2 mLacetylacetone. The solids were washed several times with 3 mL aqueousHCl in 30 mL MeOH by decanting the free liquids. The solids werecollected by vacuum filtration, washed several times on the filter withmethanol, and dried in a vacuum oven to give 7.254 g polymer (2113turnovers/Ni). The polymer was coated with 5000 ppm Irganox 1010 byevaporating an acetone slurry and drying in a vacuum oven. The polymerwas pressed at 290° C. into a transparent, colorless, toughfilm. DSC (0°to 320° C., 20° C./min, second heat) T_(g) =94° C., T_(m) (onset toend)=189° to 274° C., heat of fusion=18 J/g.

Example 450

Bis(benzonitrile)palladium dichloride (0.385 g, 1.00 mmol) and(2,6-iPrPh)₂ DABMe₂ (0.405 g, 1.00 mmol) were weighed into a glass vialinside a dry box. Dichloromethane (8 mL) was added to give a dark orangesolution. Upon standing, the solution gradually lightened in color.Cyclohexane was added to precipitate an orange solid. The solids werecollected by vacuum filtration, washed several times with cyclohexane,and dried under vacuum to give 0.463 g (80%) of the complex (2,6-iPrPh)₂DABMe₂)PdCl₂. ¹ H NMR (300 MHz, CD₂Cl₂, referenced to solvent peak at5.32 ppm): 1.19 (d, 12H, CH₃ --CHAr--CH₃), 1.45 (d, 12H, CH₃--CHAr--CH--), 2.07 (s, 6H, (CH₃ --C═N--Ar), 3.07 (m, 4H, (CH₃)₂--CH--Ar), 7.27 (d, 4H, meta ArH), 7.38 (t, 2H, para ArH).

Example 451

A sample of polycyclopentene prepared in a similar fashion to Example317 gave a transparent, brown, tough film when pressed at 290° C. DSC(25° to 330° C., 10° C./min, second heat): T₆ =98° C., T_(m) (onset toend)=174 to 284° C., heat of fusion 26 J/g. A 5 g sample that was moldedat 280° C. into a test specimen suitable for an apparatus that measuresthe response to changes in pressure, volume and temperature, and thedata output was used to calculate the following physical properties.Specific gravity, g/cm³,at temperature (°C.): 1.033 (30), 1.010 (110°C.), 0.887 (280), 0.853 (350). Bulk compression modulus, MPa, attemperature (°C.): 3500 (30), 2300 (110), 1500 (170). The coefficient oflinearthermal expansion was 0.00009° C.¹ between 30° and 110° C.

Example 452

A solution of { (2,6-i-PrPh)₂ DABMe₂ ! PdCH₂ CH₂ CH₂ C(O)OCH₃ }+SbF₆-(1.703 g) in 1.5 L CH₂ Cl₂ was transferred under nitrogen to a nitrogenpurged 1 gallon Hastalloy® autoclave. The autoclave was charged with 300g of propylene and stirred for 24 h while maintaining the temperature at25° C. The pressure was then vented. The polymer product was floating onthe solvent. Most of the solvent was removed in vacuo, and thepolymerwas dissolved in minimal CHCl₃ and then reprecipitated by addition ofexcess acetone. The polymer was dried in vacuo at 60° C. for three daysto give 271 g of green rubber. Quantitative ¹³ C NMR analysis, branchingper 1000 CH₂ : Total methyls (365), ≧Butyl and end of chains (8), CHCH₂CH (CH₃)₂ (31), --(CH₂)_(n) CH (CH₃)₂ n≧2 (25). Based on thetotalmethyls, the fraction of 1,3-enchainment is 38%. Analysis ofbackbone carbons (per 1000 CH₂): δ⁺ (138), δ⁺ /γ (1.36).

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR data    TCB, 120 C., 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    47.1728  14.6401    46.7692  9.89618    46.3285  13.3791    45.8719  7.94399    45.4684  11.1421    45.2719  7.80142    44.4754  7.11855    39.1923  29.1488    38.2791  14.2142    38.1304  18.7602    37.9074  14.9366    37.6631  15.0761    37.2809  39.5816    35.5074  8.29039    34.865   9.75536    34.5889  14.9541    34.2915  24.0579    33.2455  9.86797    32.9747  19.2516    30.6013  52.6926    30.134   55.0735     γ    30.0066  25.1831     γ    29.7518  144.066     δ.sup.+    29.3217  12.2121     3B.sub.4    28.2013  51.5842    27.9783  39.5566    27.5376  33.189    27.373   35.5457    27.1659  47.0796    27.0438  42.1247    25.6315  21.6632     terminal methine of XXVIII    23.3589  15.3063     Methyl of XXVIII and XXIX, 2B.sub.4,                         2B.sub.5.sup.+, 2EOC    23.0722  18.4837     Methyl of XXVIII and XXIX, 2B.sub.4,                         2B.sub.5.sup.+, 2EOC    22.5306  77.0243     Methyl of XXVIII and XXIX, 2B.sub.4,                         2B.sub.5.sup.+, 2EOC    21.1129  7.78367    20.5554  26.9634     1B.sub.1    20.4386  30.3105     1B.sub.1    20.0085  22.478      1B.sub.1    19.743   46.6467     1B.sub.1    13.8812  9.03898     1B.sub.4.sup.+, 1EOC    ______________________________________

Example 43

A 250 mL Schlenk flask was charged with 10 mg of (2,6-i-PrPh)₂ DABH₂!NiBr₂ (1.7×10⁻⁵ mol), and 75 mL of dry toluene. The flask was cooled to0° C. and filled with propylene (1atm) before addition of 1.5 mL of a10% MAC solution in toluene. After 45 min, acetone and water were addedto quench the reaction. Solid polypropylene was recovered from the flaskand washed with 6M HCl, H₂O, and acetone. The resulting polymer wasdried under high vacuum overnightto yield 1.2 g (2300 TO/h)polypropylene. Differential scanning calorimetry: T_(g) =-190° C. GPC(trichlorobenzene, 135° C., polystyrene reference): Mn=32,500;Mw=60,600; Mw/Mn=1.86. Quantitative ¹³ C NMR analysis, branching per1000 CH₂ : Total methyls (813),Based on the total methyls, the fractionof 1,3-enchainment is 7%. Analysisof backbone carbons (per 1000 CH₂): δ⁺(3), δ⁺ /γ (0.4).

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR data    TCB, 120 C., 0.05M CrAcAc           Freq ppm                  Intensity    ______________________________________           47.194 18.27           46.9922                  21.3352           46.8276                  35.7365           46.2011                  27.2778           45.4153                  8.55108           43.5356                  2.71929           42.925 3.37998           41.5551                  2.63256           38.826 3.03899           38.4012                  10.2858           38.0561                  8.50185           37.626 7.10732           37.4879                  6.55335           37.2755                  9.25058           36.1021                  4.48005           35.3057                  14.5319           34.4986                  11.1193           33.219 9.43548           32.9375                  4.94953           32.242 3.16177           30.8349                  24.1766           30.5217                  19.8151           30.0916                  3.70031           28.1111                  144           27.5217                  13.9133           27.1394                  3.83857           24.5005                  6.94946           21.0439                  5.25857           20.5342                  40.8641           20.0191                  60.4325           19.8758                  63.0429           16.9236                  6.47935           16.3926                  5.92056           14.9006                  10.6275           14.513 3.39891    ______________________________________

Example 454

Preparation of (2-t-BuPh)₂ DABAn. A Schlenk tube was charged with2-t-butylaniline (3.00 mL, 19.2 mmol) and acenaphthenequinone (1.71 g,9.39 mmol). The reagents were partially dissolved in 50 mL of methanol(acenaphthenequinone was not completely soluble) and 1-2 mL of formicacidwas added. An orange solid formed and was collected via filtrationafter stirring overnight. The solid was crystallized from CH₂ Cl₂ (3.51g, 84.1%). ¹ H NMR (CDCl₃, 250 MHz) δ7.85 (d, 2H, J=8.0 Hz, BIAn:H_(p)), 7.52 (m, 2H, Ar: H_(m)), 7.35 (dd, 2H, J=8.0, 7.3 Hz, BIAn:H_(m)), 7.21 (m, 4H, Ar: H_(m) and H_(p)), 6.92 (m, 2H, Ar: H_(o)), 6.81(d, 2H, J=6.9 Hz, BIAn: H_(o)), 1.38 (s, 18H, C(CH₃)₃).

Example 455

Preparation of (2,5-t-BuPh)₂ DARAn. A Schlenk tube was charged with2,5-di-t-butylaniline (2.00 g, 9.74 mmol) and acenaphthenequinone (0.88g,4.8 mmol). The reagents were partially dissolved in 50 mL of methanol(acenaphthenequinone was not completely soluble) and 1-2 mL of formicacidwas added. A solid was collected via filtration after stirringovernight. Attempted crystallization from ether and from CH₂ Cl₂ yieldedanorange/yellow powder (1.75 g, 66%. ¹ H NMR (CDCl₃, 250 MHz) δ7.85 (d,2H, J=8.1 Hz, BIAn: H_(p)), 7.44 (d, 2H, J=8.4 Hz, Ar: H_(m)), 7.33 (dd,2H, J=8.4, 7.3 Hz, BIAn: H_(m)), 7.20 (dd, 2H, J=8.1, 2.2 Hz, Ar:H_(p)), 6.99 (d, 2H, J=2.2 Hz, Ar: H_(o)), 6.86 (d,2H, J=7.0 Hz, BIAn:H_(o)), 1.37, 1.27 (s, 18H each, C(CH₃)₃).

Example 456

Preparation of (2-t-BuPh)₂ DABAn!NiBr₂. A Schlenk tube was charged with0.202 g (0.454 mmol) of (2-t-BuPh)₂ DABAn, which was then dissolved in15 mL of CH₂ Cl₂. This solution was cannulatedonto a suspension of(DME)NiBr₂ (0.135 g, 0.437 mmol) in 10 mL of CH₂ Cl₂. The reactionmixture was allowed to stir overnight resulting in a deep red solution.The solution was filtered and the solvent evaporated under vacuum. Theresidue was washed with ether (2×10 mL) and an orange/rust solid wasisolated and dried under vacuum (0.18 g, 62%).

Example 457

Preparation of (2,5-t-BuPh)₂ DABAn!NiBr₂. A Schlenk tube was chargedwith 0.559 g (1.00 mmol) of (2,5-t-BuPh)₂ DABAn, 0.310 g (1.00 mmol) of(DME)NiBr₂ and 35 mL of CH₂ Cl₂. The reaction mixture was allowed tostir overnight. The solution was filtered and the solvent evaporatedunder vacuum. The residue was washed with etherand resulted in an orangesolid which was dried under vacuum (0.64 g, 83%).

Example 458

Preparation of highly chain-straightened polypropylene with a low T_(g).The complex (2-t-BuPh)₂ DABAn!NiBr₂ (0.0133 g, 2.0×10⁻⁵ mol) was placedinto a flame-dried 250 mL Schlenk flask which was then evacuated andback-filled with propylene. Freshly distilled toluene (100 mL) was addedvia syringe and the resulting solution was stirred in a water bath atroom temperature. Polymerization was initiated by addition ofmethylaluminoxane (MAO; 1.5 mL 10% soln in toluene) and a propyleneatmosphere was maintained throughout the course of the reaction. Thereaction mixture was stirred for two hours at constant temperaturefollowed by quenching with 6M HCl. Polymer was precipitated from theresulting solution with acetone, collected, washed with water andacetone, and dried under vacuum. Yield=1.41 g. DSC: T_(g) -53.6° C.,T_(m) -20.4° C. (apparent Tm is a small shoulder on the Tg).Quantitative ¹³ C NMR analysis, branching per 1000 CH₂ : Total methyls(226), ≧Butyl and end of chains (8.5), CHCH₂ CH(CH₃)₂ (2.3), --(CH₂)_(n)CH(CH₃)₂ n≧2 (12.1). Based on the total methyls, the fraction of1,3-enchainment is 53%. Analysis of backbone carbons (per 1000CH₂): δ⁺(254), δ⁺ /γ (1.96).

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR Data    TCB, 120C, 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    46.3126  6.77995    46.079   6.56802    45.463   7.82411    45.2453  6.98049    39.1764  8.95757    38.4384  5.42739    38.1145  20.5702    37.8755  18.8654    37.626   19.2917    37.2702  128.202    35.0773  6.30042    34.5304  19.5098    34.2543  38.6071    33.7816  4.3205    33.2986  16.3395    32.9588  72.1002    31.934   10.626    31.419   5.57124    30.5907  41.727    30.1287  134.412    29.7518  351.463    29.3217  9.58971    28.1589  21.1043    27.9677  17.7659    27.5589  44.1485    27.3783  25.0491    27.1766  119.562    27.0226  52.4586    ˜25.6           terminal methine of XXVIII    24.5908  8.69462    24.4315  9.27804    22.5253  30.7474      region of methyls of XXVIII                          and XXIX, 2B.sub.4 +, 2 EOC    20.4333  20.0121      1B.sub.1    19.7271  103.079      1B.sub.1    14.7679  5.0022    14.4068  4.56246    13.8812  12.3077      1B.sub.4 +, 1 EOC    ______________________________________

Example 459

Preparation of highly chain-straightened polypropylene with a low T_(g).The complex (2,5-t-BuPh)₂ DABAn!NiBr₂ (0.0155 g, 2.0×10⁻⁵ mol) wasplaced into a flame-dried 250 mL Schlenk flask which was then evacuatedand back-filled with propylene. Freshly distilled toluene (100 mL) wasadded via syringe and the resulting solution was stirred in a water bathat room temperature. Polymerization was initiated by addition of 1.5 mLof a 10% MAO solution in toluene, and a propylene atmosphere wasmaintained throughout the course of the reaction. The reaction mixturewas stirred for two hours at constant temperature followed by quenchingwith 6M HCl. Polymer was precipitated from the resulting solution withacetone, collected, washed with water andacetone, and dried undervacuum. Yield=0.75 g. DSC: T_(g) -53.0° C., T_(m) none observed.Quantitative ¹³ C NMR analysis, branching per 1000 CH₂ : Total methyls(307), ≧Butyl and end of chains (11.2), --CHCH₂ CH(CH₃)₂ (11.5),--(CH₂)_(n) CH(CH₃)₂, n≧2 (5.9). Based on the total methyls, thefraction of 1,3-enchainment is 43%.

Listed below are the ¹³ C NMR data upon which the above analysis isbased.

    ______________________________________    .sup.13 C NMR data    TCB, 120 C., 0.05M CrAcAc    Freq ppm Intensity    ______________________________________    46.3126  6.77995    46.079   6.56802    45.463   7.82411    45.2453  6.98049    39.1764  8.95757    38.4384  5.42739    38.1145  20.5702    37.8755  18.8654    37.626   19.2917    37.2702  128.202    35.0773  6.30042    34.5304  19.5098    34.2543  38.6071    33.7818  4.3205    33.2986  16.3395    32.9588  72.1002    31.934   10.626    31.419   5.57124    30.5907  41.727    30.1287  134.312    29.7518  351.463    29.3217  9.58971    28.1589  21.1043    27.9677  17.7659    27.5589  44.1485    27.3783  25.0491    27.1766  119.562    27.0226  52.4586    ˜25.6           terminal methine of XXVIII    24.5908  8.69462    24.4315  9.27804    22.5253  30.7474      region of methyls of XXVIII                          and XXIX, 2B.sub.4.sup.+, 2EOC    20.4333  20.0121      1B.sub.1    19.7271  103.079      1B.sub.1    14.7679  5.0022    14.4068  4.56246    13.8812  12.3077      1B.sub.4.sup.+, 1EOC    ______________________________________

Example 460

Preparation of highly chain-straightened poly-1-hexene with a highT_(m).A flame-dried 250 mL Schlenk flask under a nitrogen atmosphere wascharged with 40 mL of freshly distilled toluene, 0.0133 g of (2-t-BuPh)₂DABAn!NiBr₂ (2.0×10⁻⁵ mol), 5.0 mL of 1-hexene, and 55 mL more toluene(100 mL total volume of liquid). Polymerization was initiatedby additionof 2.0 mL of MAO (10% solution in toluene). The reaction mixture wasstirred for 11.5 hours at room temperature followed by quenching with 6MHCl. Polymer was precipitated from the resulting solution with acetone,collected via filtration, washed with water and acetone, and dried undervacuum. Yield=1.84 g. DSC: T_(g) -44.8° C., T_(m) 46.0° C.

Example 461

Preparation of highly chain-straightened poly-1-hexene with a highT_(m).A flame-dried 250 mL Schlenk flask under a nitrogen atmosphere wascharged with 40 mL of freshly distilled toluene, 0.0155 g of(2,5-t-BuPh)₂ DABAn!NiBr₂ (2.0×10⁻⁵ mol), 5.0 mL of 1-hexene, and 55 mLmore toluene (100 mL total volume of liquid). Polymerization wasinitiatedby addition of 2.0 mL of MAO (10% solution in toluene). Thereaction mixture was stirred for 11.5 hours at room temperature followedby quenching with 6M HCl. Polymer was precipitated from the resultingsolution with acetone, collected via filtration, washed with water andacetone, and dried under vacuum. Yield=1.07 g. DSC: T_(g) -54.7° C.,T_(m) 12.5° C.

Example 462

Preparation of (2-t-BuPh)₂ DABAn!PdMe₂ from (1,5-cyclooctadiene)PdMe₂.The Pd(II) precursor (1,5-cyclooctadiene)PdMe₂ ((COD)PdMe₂) was preparedaccording reported procedures (Rudler-Chauvin, M.; Rudler, H. J.Organomet. Chem., 1977, 134, 115.) and was handled using Schlenktechniques at temperatures of -10° C. or below. A flame-dried Schlenktube was charged with 0.056 g (0.229 mmol) of (COD)PdMe₂ and cooled to-40° C. in a dry ice/isopropanol bath. The solid was dissolved in 10 mLof ether, and the diimine (2-t-BuPh)₂ DABAn (0.106 g, 0.238 mmol) wascannulated onto the stirring solution as a slurry in 15 mL of ether. Thereaction waswarmed to 0° C. and stirring was continued for two hours.The reaction flask was stored at -30° C. for several days and resultedin the formation of a green precipitate which was isolated viafiltration.The supernatant was pumped dry under high vacuum and alsoresulted in a green solid. Both solids were determined to be (2-t-BuPh)₂DABAn!PdMe₂ by ¹ H NMR spectroscopy. Isolated yield=0.083 g (0.143 mmol,62.4%).

Example 463

Preparation of (2,5-t-BuPh)₂ DABAn!PdMe₂ from (1,5-cyclooctadiene)PdMe₂.The Pd(II) precursor (1,5-cyclooctadiene)PdMe₂ ((COD)PdMe₂) was preparedaccording reported procedures (Rudler-Chauvin, M.; Rudler, H. J.Organomet. Chem., 1977, 134, 115.) and was handled using Schlenktechniques at temperatures of -10° C. or below. A flame-dried Schlenktube was charged with 0.102 g (0.417 mmol) of (COD)PdMe₂ and cooled to-30° C. in a dry ice/isopropanol bath. The solid was dissolved in 10 mLof ether, and the diimine (2,5-t-BuPh)₂ DABAn (0.234 g, 0.420 mmol) wascannulated onto the stirring solution as a slurry in 40 mL of ether. Thereaction waswarmed to 0° C. and stirring was continued for four hours.The reaction flask was stored at -30° C. overnight. The resulting darkgreen solution was filtered and the solvent was pulled off under highvacuum to give a dark green powder. Analysis by ¹ H NMR spectroscopyshowed the solid to be consistent with the desired product,(2,5-t-BuPh)₂ DABAn!PdMe₂. Yield=0.256 g (0.370 mmol, 88.7%).

Example 464

In a dry box, polymer from Example 469 (0.57 g), THF (10.10 g) andacetic anhydride (0.65 g) were placed in a 20 mL vial equipped with astirring bar. After one hour at room temperature, the vial was removedfrom the drybox and the polymerization terminated by the addition ofTHF, water and ether. The organic phase was separated, washed with water(2×), dried over anhydrous sodium sulfate, concentrated at reducedpressure and then dried under vacuum, affording 4.44 g of polymer. GPCanalysis (PS STD.): Mn=17600, Mw=26000, PD=1.48.

Example 465 Preparation of CH₂ ═CH(CH₂)₂ CHICH₂ (CF₂)₂ OCF₂ CF₂ SO₂ F

A mixture of 72 g of hexadiene, 127.8 g of ICF₂ CF₂ OCF₂ CF₂ SO₂ F, 7.0g of Cu powder and 180 mL of hexane was stirred at 90° C. overnight.Solids were removed by filtration and washed with hexane. After removalof volatiles, residue was distilled to give 115.3 g of product, bp 80°C./210 Pa. ¹⁹ F NMR: +45 (t, J=6.0 Hz, 1 F), -82.7 (m, 2 F), -88.1 (dt,J=42.5 Hz, J=12.6 Hz, 1 F), -88.7 (dt, J=45.5 Hz, J=12.6 Hz, 1 F),-112.7 (m, 2 F), -115.9 (ddd, J=2662.2 Hz, J=30.0 Hz, J=8.2 Hz, 1 F),-118.9 (ddd, J=262.2 Hz, J=26.8 Hz, J=7.4 Hz, 1 F).

Example 466 Preparation of CH₂ ═CH(CH₂)₄ (CF₂)₂ OCF₂ CF₂ SO₂ F

To a stirred solution of 100 g of CH₂ ═CH(CH₂)₂ CHICH₂ (CF₂)₂ OCF₂ CF₂SO₂ F and 200 mL of ether was added 63 g of Bu₃ SnH at room temperature.After the addition was complete, the reaction mixture was refluxed for 4hours and then cooled with ice water. Excess of Bu₃ SnH was destroyed byaddition of iodine. After being diluted with 200 mL of ether, thereactionmixture was treated with a solution of 25 g of KF in 200 mL ofwater for 30min. The solids were removed by filtration through a funnelwith silica geland washed with ether. The ether layer was separated andwashed with water,aqueous NaCl solution and dried over MgSO₄. Afterremoval of the ether, residue was distilled to give 54.7 g of product,bp 72° C./1.3 kPa, and 12.2 g of starting material.

¹⁹ F NMR: +45 (m, 1 F), -82.7 (m, 2 F), -88.0 (m, 2 F), -112.6 (m, 2 F),-118.6 (t, J=18.4 Hz, 2 F).

Example 467 Preparation of CH₂ ═CH(CH₂)₄ (CF₂)₄ OCF₂ CF₂ SO₂ F

A mixture of 24 g of hexadiene, 53 g of I(CF₂)₄ OCF₂ CF₂ SO₂ F, 3.0 g ofCu powder and 60 mL of hexane was stirred at70° C. overnight. Solidswere removed by filtration and washed with hexane. After removal ofvolatiles, residue was distilled to give 115.3 g of adduct, CH₂═CH(CH₂)₂ CHICH₂ (CF₂)₄ OCF₂ CF₂ SO₂ F, bp 74° C./Pa. ¹⁹ F NMR: +45.5(m, 1 F), -82.4 (m, 2 F), -83.5 (m, 2 F), -112.2 (dm, J=270 Hz, 1 F),-112.6 (m, 2 F), -115.2 (dm, J=270 Hz, 1 F), -124.3 (s, 2 F), -125.5 (m,2F).

To stirred solution of 47 g of CH₂ ═CH(CH₂)₂ CHICH₂(CF₂)₄ OCF₂ CF₂ SO₂ Fand 150 mL of ether was added 27 g of Bu₃ SnH at room temperature. Afterthe addition was complete, the reaction mixture was stirred overnight.Excess of Bu₃ SnH was destroyed by addition of iodine. After beingdiluted with 150 mL of ether, the reaction mixture was treated with asolution of 20 g of KF in 100 mL of water for 30 min. The solids wereremoved by filtration through a funnel with silica gel and washed withether. The ether layer was separated and washed with water, aqueous NaClsolution and dried over MgSO₄. After removal of the ether, residue wasdistilled to give 24.7g of product, bp 103° C./1.3 kPa. ¹⁹ F NMR: +45.4(m, 1 F), -82.4 (m, 2 F), -83.5 (m, 2 F), -112.6 (t, J=2.6 Hz, 2 F),-115.1 (t, J=15Hz, 2 F), -124.3 (s, 2 F), -125.7 (t, J=14 Hz, 2 F).HRMS: calcd for C₁₂ H₁₁ F₁₃ SO₃ : 482.0221. Found: 482.0266.

Example 468 Hydrolysis of Copolymer

Copolymer containing 8.5 mol % of comonomer (1.5 g) was dissolved in 30mL of THF at room temperature. KOH (0.5 g) in 5 mL of ethanol and 3 mLof water was added and the resulting mixture was stirred at roomtemperature for six hours. After removal of the solvent, residue wastreated with diluted HCl for 70 hours and then filtered to give solidswhich were washed with water, HCl and dried under full vacuum at 70° C.for two days to give 1.4 g solid.

Example 469 Hydrolysis of Copolymer

A mixture of 10.6 g of copolymer 5.0 g of KOH, 2 mL of water, 30 mL ofethanol and 30 mL of THF was stirred at room temperature overnight andat 60° to 70° C. for 5 hours. After removal of a half of solvents,residue was treated with Conc. HCl to give rubbery material, which waspoured into a blender and blended with water for 30 min. Filtration gavesolids, which were washed with conc. HCl, and water and dried undervacuum at 60° C. overnight to give 8.7 g of dark rubbery material. ¹⁹ FNMR(THF): -82.8 (br, 2F), -88.5 (br, 2F), -118.3 (br, 2F), -118.5 (br,2F).

Example 470 Hydrolysis of Homopolymer

A solution of 2.0 g of KOH in 25 mL of ethanol and 2 mL of waster wasaddedto a flask with 3.0 g of homopolymer. The resulting heterogeneousmixture was stirred at room temperature overnight and heated to 60° C.for 2 hours. After removal of one-half of liquid, the reaction mixturetreatedwith 40 mL of conc. HCl for 30 min. Filtration gave white solidswhich werewashed with conc. HCl, and distilled water and dried undervacuum at 60°-70° C. for 24 hours to give 2.9 g of white powder.

Example 471

1-Octadecene (8 mL, 8 vol %) was added to a suspension of (2,6-i-PrPh)₂DABAn!NiBr₂ (12 mg, 1.7×10⁻⁵ mol) in 100 mL of dry toluene. The flaskwas cooled to -1° C. using an Endocal® refrigerated circulating bath and2.5 mL of a 7% MMAO solution in heptane was added. After stirring thereaction for 40 min, theflask was filled with propylene (1 atm) andstirred for 20 minutes. The propylene was removed in vacuo and thereaction allowed to continue for anadditional 40 min. Acetone and waterwere added to quench the polymerization and precipitate the polymer. Theresulting triblock polymerwas dried under high vacuum overnight to yield650 mg of a rubbery solid. GPC (trichlorobenzene, 135° C., polystyrenereference): M_(n) =60,100; M_(w) =65,500; M_(w) /M_(n) =1.09. DSCanalysis: Two melt transitions were observed. T_(m) =8° C. (32 J/g),T_(m) =37° C. (6.5 J/g). ¹ H-NMR analysis (CDCl₃): signals attributableto repeat units of propylene and 1-octadecene were observed.

Example 472 Preparation of (2-i-Pr-6-MePh)₂ DABAn

A Schlenk tube was charged with 2-isopropyl-6-methylaniline (5.00 mL,30.5 mmol) and acenaphthenequinone (2.64 g, 14.5 mmol). The reagentswere partially dissolved in 50 mL of methanol (acenaphthenequinone wasnot completely soluble) and 1-2 mL of formic acid was added. Anorange/yellow solid was collected via filtration after stirringovernight, and was washed with methanol and dried under vacuum.

Example 473 Preparation of (2-i-Pr-6-MePh)₂ DABMe₂

A Schlenk tube was charged with 2-isopropyl-6-methylaniline (5.00 mL,30.5 mmol) and 2,3-butanedione (1.31 mL, 14.9 mmol). Methanol (5 mL) andone drop of concentrated HCl were added and the mixture was heated toreflux with stirring for 30 minutes. The methanol and remaining dionewere removed under vacuum to give a dark, oily residue. The oil waschromatographed on a silica gel column using 10% ethyl acetate: 90%hexaneas the eluent. The fractions containing the pure diimine werecombined and concentrated. The remaining solvents were removed undervacuum to give a pale yellow powder (0.9217 g, 17.75%).

Example 474 Preparation of (2-i-Pr-6-MePh)₂ DABAn!NiBr₂

Under inert conditions, a flame-dried Schlenk tube was charged with 0.50g (1.13 mmol) of (2-i-Pr-6-MePh)₂ DABAn, 0.34 g (1.10 mmol) of(DME)NiBr₂ and 25 mL of CH₂ Cl₂. The reaction mixture was allowed tostir overnight. The solution was filtered and the solvent removed undervacuum. The residue was washed with ether (4×10 mL) togive anorange/yellow powder which was dried under vacuum overnight (0.68 g,94%).

Example 475 Preparation of (2-i-Pr-6-MePh)₂ DABMe₂ !NiBr₂

Under inert conditions, a flame-dried Schlenk tube was charged with0.3040 g (0.8722 mmol) of (2-i-Pr-6-MePh)₂ DABMe₂, 0.2640 g (0.8533mmol) of (DME)NiBr₂ and 25 mL of CH₂ Cl₂. The reaction mixture wasallowed to stir overnight. A solid was collected via filtration andwashed with ether (2×10 mL). Upon sitting, more solidprecipitated fromthe supernatant. This precipitate was isolated via filtration, washedwith ether, and combined with the originally isolated product. Thecombined yellow/orange solids were dried under vacuum overnight (0.68 g,94%).

Example 476

Under a nitrogen atmosphere, the complex (2-i-Pr-6-MePh)₂ DABAn!NiBr₂(0.0099 g, 1.5×10⁻⁵ mol) was placed into a flame-dried 250 mL Schlenkflask which was then evacuated and back-filled with propylene. Freshlydistilled toluene (100 mL) was added via syringe and the resultingsolution was stirred for five minutes at room temperature.Polymerization was initiated with addition of methylaluminoxane (MAO;1.5 mL 10% solution in toluene) and a propylene atmosphere wasmaintained throughout the course of the reaction. The reaction wasstirred for two hours at constant temperature, at which pointthepolymerization was by quenched with 6M HCl. Polymer was precipitatedfrom the resulting solution with acetone, washed with water and acetone,and dried under vacuum. Yield=3.09 g. DSC: T_(g) -31.2° C. GPC: M_(n)=142,000; M_(w) =260,000; M_(w) /M_(n) =1.83.

Example 477

Under a nitrogen atmosphere, the complex (2-i-Pr-6-MePh)₂ DABMe₂ !NiBr₂(0.0094 g, 1.5×10⁻⁵ mol) was placed into a flame-dried 250 mL Schlenkflask which was then evacuated and back-filled with propylene. Freshlydistilled toluene (100 mL) was added via syringe and the resultingsolution was stirred for five min at room temperature. Polymerizationwas initiated with addition of methylaluminoxane (MAO; 1.5 mL 10%solution in toluene) and a propylene atmosphere was maintainedthroughout the course of the reaction. The reaction was stirred for twohours at constant temperature, at which point the polymerization was byquenched with 6M HCl. Polymer was precipitated from the resultingsolutionwith acetone, washed with water and acetone, and dried undervacuum. Yield=1.09 g. DSC: T_(g) -36.1° C. GPC: M_(n) =95,300; M_(w)=141,000; M_(w) /M_(n) =1.48.

Example 478

Under a nitrogen atmosphere, a flame-dried 250 mL Schlenk flask waschargedwith 40 mL of freshly distilled toluene, 0.0133 g (2.0×10⁻⁵mol)of (2-i-Pr-6-MePh)₂ DABAn!NiBr₂, 10.0 mL of 1-hexene, and 50 mL moretoluene (100 mL total volume of liquid). The mixture was stirred inaroom temperature water bath for 10 minutes and polymerization wasinitiatedwith addition of 2.0 mL of MAO (10% solution in toluene). Thereaction mixture was stirred for one hour at room temperature and wasquenched with6M HCl. Polymer was precipitated from the resultingsolution with acetone, collected via filtration, washed with water andacetone, and dried under vacuum. Yield=3.23 g. DSC: T_(g) -58.0° C.,T_(m) -16.5°C.

Example 479

Under a nitrogen atmosphere, a flame-dried 250 mL Schlenk flask waschargedwith 40 mL of freshly distilled toluene, 0.0125 g (2.0×10⁻⁵mol)of (2-i-Pr-6-MePh)₂ DABMe₂ !NiBr₂, 10.0 mL of 1-hexene, and50 mLmore toluene (100 mL total volume of liquid). The mixture was stirredina room temperature water bath for 10 min and polymerization wasinitiated with addition of 2.0 mL of MAO (10% solution in toluene). Thereaction mixture was stirred for 22 h at room temperature and wasquenchedwith 6M HCl. Polymer was precipitated from the resultingsolution with acetone, collected via filtration, washed with water andacetone, and dried under vacuum. Yield 2.10 g. DSC: T_(g) -56.4° C.,T_(m) 0.2° C.

Example 480

Under a nitrogen atmosphere, a flame-dried 250 mL Schlenk flask waschargedwith 40 mL of freshly distilled toluene, 0.0133 g (2.0×10⁻⁵mol)of (2-t-BuPh)₂ DABAn!NiBr₂, 10.0 mL of 1-hexene, and 50 mL moretoluene (100 mL total volume of liquid). The mixture was stirred in anisopropanol bath maintained at approximately -10° to -12° C., andpolymerization was initiated with addition of 2.5 mL of MMAO(7.2%solution in heptane). The reaction mixture was stirred for twohours at constant temperature and was quenched with acetone/water/6MHCl. The mixture was added to acetone to precipitate the polymer. Aftersettling overnight the polymer was collected via filtration, washed withwater and acetone, and dried under vacuum. Yield=0.35 g. DSC: (two broadmelt transitions observed) T_(m) (1) 34.3° C., T_(m) (2) 66.4° C. Basedon the ¹ H NMR spectrum, the polymer contains 41 methyl branches/1000carbons (theoretical=55.5 Me/1000 C.), indicating a high degree of chainstraightening.

Example 481

Under a nitrogen atmosphere, a flame-dried 250 mL Schlenk flask waschargedwith 25 mL of freshly distilled toluene, 0.0133 g (2.0×10⁻ 5 mol)of (2-t-BuPh)₂ DABAn!NiBr₂, 63 mL more toluene, and 12.0 mL of1-octadecene (100 mL total volume of liquid). The flask was cooled to-10° C. in a CO₂ /isopropanol bath and stirred at this temperature forseveral minutes. The temperature was maintained at approximately -10° C.throughout the reaction by continually addingdry ice as needed.Polymerization of 1-octadecene was initiated with addition of 2.5 mL ofMMAO (7.2% solution in heptane). At 2 h, 10 min the reaction flask wastwice evacuated and back-filled with propylene. The polymerization wasstirred under one atmosphere of propylene for 20 min. The propylene wasremoved by repeatedly evacuating the flask and back-filling with argonuntil propylene evolution from the solution was nolonger apparent. Thepolymerization was allowed to continue stirring in thepresence of theremaining 1-octadecene until a total elapsed time of five hours wasreached. The reaction was quenched with acetone/water/6M HCl. Polymerwas precipitated in methanol/acetone, collected via filtration, washedwith water and acetone, and dried under vacuum. Yield=1.03 g. DSC: T_(g)8.0° C., T_(m) 53.3° C. GPC: M_(n) =55,500; M_(w) =68,600; M_(w) /M_(n)=1.24. It is believed a block copolymer was formed.

Example 482 Preparation of (2-t-BuPh)₂ DABAn!PdMe(Et₂ O)BAF⁻

Under inert conditions, a flame-dried Schlenk tube was charged with0.1978 g (3.404×10⁻⁴ mol) of (2-t-BuPh)₂ DABAn!PdMe₂ and 0.3451 g(3.408×10⁻⁴ mol) of H⁺ (Et2O)₂ BAF⁻. The Schlenk tube was cooled to -78°C. and 10 mL of ether was added. The Schlenk tube was transferred to anice water bath and the reaction was stirred until the solids weredissolved and the color of the solution became deep red. The ether wasthen removed under vacuum to give a red, glassy solid that was crushedinto a powder (yield was quantitative).

Example 483 Preparation of (2,5-t-BuPh)₂ DABAn!PdMe(Et₂ O)BAF⁻

Following the procedure of Example 482, a red solid with the structure(2,5-t-BuPh)₂ DABAn!PdMe(Et₂ O)BAF⁻ was obtained (quantitative yield).

Example 484 Preparation of (2-t-BuPh)₂ DABMe₂ !PdMe(NCMe)BAF⁻

Under inert conditions, a flame-dried Schlenk tube was charged with0.1002 g (0.378 mmol) of (COD)PdMeCl and 0.3348 g (0.378 mmol) of NaBAF.The Schlenk tube was cooled to -30° C. and 25 mL of CH₂ Cl₂ and 0.10 mLof NCMe were added via syringe. The reaction was stirred for two h at-20° to -30° C. The resulting colorless solution was filtered intoanother cooled Schlenk tube, 20 mL of hexane was added, and the solventswere removed under vacuum to give a white powder isolated(COD)PdMe(NCMe)BAF⁻ !. This cationic precursor was combinedwith 0.138 g(0.396 mmol) of (2-t-BuPh)₂ DABMe₂ in 50 mL of NCMe.The reaction mixturewas stirred overnight at room temperature. The solution was filtered andextracted with hexane (3×10 mL), and the solvents were removed undervacuum. The resulting yellow oil was dissolvedin CH₂ Cl₂ /hexane and thesolvents were removed under vacuum to give a glassy solid that wascrushed into a powder. Two isomers were observed in solution by ¹ H NMRspectroscopy. These two isomers arisefrom the coordination of theunsymmetrically substituted ligand in either the cis or trans fashion inregard to the t-butyl groups relative to the square plane of thecomplex.

Example 485 Polymerization of ethylene with (2-t-BuPh)₂ DABAn!PdMe(Et₂O)BAF⁻

A flame-dried 250 mL Schlenk flask was charged with 0.1505 g (1.001×10⁻⁴mol) of (2-t-BuPh)₂ DABAn!PdMe(Et₂ O)BAF⁻ in the glove box. The flaskwas twice evacuated and back-filled with ethylene and then cooled to-60° C. The solid was dissolved in 100 mL of CH₂ Cl₂ and the flask wasallowed to warmto room temperature with stirring under an atmosphere ofethylene. After stirring for 23 h the polymerization was quenched withmethanol. The solvent was removed under reduced pressure and the polymerwas dissolved in petroleum ether and filtered through silica gel. Thefiltrate was concentrated and the remaining solvent was removed undervacuum to give a clear, colorless, viscous liquid. Yield=0.2824 g. ¹ HNMR analysis: 125 Me/1000 CH₂.

Example 486

A flame-dried 250 mL Schlenk flask was charged with 0.1621 g (1.003×10⁻⁴mol) of (2,5-t-BuPh)₂ DABAn!PdMe(Et₂ O)BAF⁻ in the glove box. The flaskwas twice evacuated and back-filled with ethylene and then cooled to-60° C. The solid was dissolved in 100 mL of CH₂ Cl₂ and the flask wasallowed to warmto room temperature with stirring under an atmosphere ofethylene. After stirring for 23 h the polymerization was quenched withmethanol. The solvent was removed under reduced pressure and the polymerwas dissolved in petroleum ether and filtered through silica gel. Thefiltrate was concentrated and the remaining solvent was removed undervacuum to give a clear, colorless, viscous liquid. Yield=0.2809 g. ¹ HNMR analysis: 136 Me/1000 CH₂.

Example 487

A flame-dried 250 mL Schlenk flask was charged with 0.1384 g (1.007×10⁻⁴mol) of (2-t-BuPh)₂ DABMe₂ !PdMe(NCMe)BAF⁻ in the glove box. The flaskwas twice evacuated and back-filled with ethylene and then cooled to-60° C. The solid was dissolved in 100 mL of CH₂ Cl₂ and the flask wasallowed to warmto room temperature with stirring under an atmosphere ofethylene. After stirring for 23 h the polymerization was quenched withmethanol. The solvent was removed under reduced pressure and the polymerwas dissolved in petroleum ether and filtered through silica gel. Thefiltrate was concentrated and the remaining solvent was removed undervacuum to give a clear, colorless, viscous liquid. Yield=2.40 g. ¹ H NMRanalysis: 123Me/1000 CH₂.

Example 488

Under inert conditions, a Schlenk tube was charged with 0.0142 g(1.02×10⁻⁵ mol) of (2-t-BuPh)₂ DABAn!PdMe(Et₂ O)BAF⁻. The Schlenk tubewas cooled to -78° C. and the solid was dissolved in 30 mL of CH₂ Cl₂. A300 mL autoclave was charged with 70 mL of CH₂ Cl₂ under an ethyleneatmosphere. The cold catalyst solution was quickly transferred viacannula into the Parr® reactor and the reactor was pressurized to 172kPa (absolute). The polymerization was stirred for 20 h and the ethylenepressure was released. The red/orange solution was transferred and thesolvent was removed under vacuum. A small amount of polyethyleneremained after dryingunder vacuum overnight. Yield=0.17 g. ¹ H NMRanalysis: 120 Me/1000 CH₂.

Example 489

Following the procedure described in Example 488, 1.68 g of polyethylenewas produced using 0.0140 g (1.02×10⁻⁵ mol) of (2-t-BuPh)₂ DABMe₂!PdMe(NCMe)BAF⁻. Yield=1.68 g. ¹ HNMR analysis: 114 Me/1000 CH₂.

Example 490

Under nitrogen, Ni(COD)2 (0.017 g, 0.062 mmol) and (2,4,6-MePh)₂DABAn(0.026 g, 0.062 mmol) were dissolved in 2.00 g of cyclopentene togive a purple solution. The solution was then exposed to air for severalseconds.The resulting dark red-brown solution was then put back undernitrogen, andEtAlCl₂ (1M solution in toluene, 3.0 mL, 3.0 mmol) wasadded. A cranberry-red solution formed instantly. The reaction mixturewas stirred at room temperature for 3 days, during which timepolycyclopentene precipitated. The reaction was then quenched by theaddition of methanol followed by several drops of concentrated HCl. Thereaction mixture was filtered, and the product polymer washed withmethanol and dried to afford0.92 g of polycyclopentene as an off-whitepowder. Thermal gravimetric analysis of this sample showed a weight lossstarting at 141° C.: the sample lost 18% of its weight between 141° and470° C., and the remaining material decomposed between 470° and 496° C.

Example 491

Under a nitrogen atmosphere, Ni(COD)₂ (0.017 g, 0.06 mmol) andMeC(═N-2,6-C₆ H₃ -iPr₂)CH═C(NH--C₆ H₃ -iPr₂)Me (0.025 g, 0.06 mmol) weredissolved in benzene (5.0 mL). To the resulting solution was added HBAF(Et₂ O)₂ (0.060 g, 0.06 mmol). The resulting solution was immediatelyfrozen inside a 40 mL shakertube glass insert. The glass insert wastransferred to a shaker tube, and its contents allowed to thaw under anethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C₂H₄ for 40 h at ambient temperature. The final reaction mixture containedpolyethylene, which was washed with methanol and dried; yield ofpolymer=1.37 g. Branching per 1000 CH₂ 's was determined by ¹³ C NMR (C₆D₃ Cl₃): Total methyls (10.2), Methyl (8.8), Ethyl (1.1), Propyl (0),Butyl (0), ≧Am and end of chains (3.2), ≧Bu and end of chains (0.3)

Example 492

Under a nitrogen atmosphere, Ni(COD)₂ (0.017 g, 0.06 mmol) and theligand shown below (0.025 g, 0.06 mmol) were dissolved in benzene (5.0mL). To the resulting solution was added HBAF (Et₂ O)₂ (0.060 g,0.06mmol). The resulting solution was immediately frozen inside a 40 mLshaker tube glass insert. The glass insert was transferred to a shakertube, and its contents allowed to thaw under an ethylene atmosphere. Thereaction mixture was agitated under 6.9 MPa C₂ H₄ for 18 h at ambienttemperature. The final reaction mixture contained polyethylene, whichwas washed with methanol and dried; yield of polymer=11.0 g. ##STR92##

Example 493 { (2.6-i-PrPh)₂ DABMe₂ !Pd(η³ -CHEtPh)!}BAF

In a nitrogen-filled drybox, 25 mL of Et₂ O was added to a flaskcontaining (2.6-i-PrPh)₂ DABMe₂ !PdMeCl (402 mg, 0.716 mmol) and NaBAF(633 mg, 0.714 mmol) to yield an orange solution. Styrene (110 μL, 0.960mmol, 1.35 equiv) was dissolved in ˜10 mL of Et₂ Oand the resultingsolution was added to the reaction mixture, which was then stirred for 3h. Next, the solution was filtered and the solvent was removed in vacuo:The resulting orange powder (0.93 g, 87%) was washed with hexane anddried in vacuo. ¹ H NMR (CD₂ Cl₂, 300 MHz, rt) δ7.76 (s, 8, BAF: H_(o)),7.59 (s, 4, BAF: H_(p)), 7.46-7.17(m, 9, H_(aryl)), 6.29 (d, 1, J=7.33,H_(aryl)), 5.65 (d, 1, J=6.59, H_(aryl)), 3.33, 3.13, 2.37 and 1.93(septet, 1 each, J=6.97-6.72, CHMe₂, C'HMe₂, C"HMe₂, C'"HMe₂), 3.17 (dd,1, J=11.36,3.66, CHEtPh), 2.22 and 2.17 (s, 3 each, N═C(Me)--C'(Me)═N),1.52, 1.45, 1.26, 1.26, 1.19, 1.15, 0.94 and 0.73 (d, 3 each,J=6.97-6.59, CHMeMe', C'HMeMe', C"HMeMe', C'"HMeMe'), 0.88 (t, 3,J=0.88, CH(CH₂ CH₃)Ph), 1.13 and -0.06 (m, 1 each, CH(CHH'CH₃)Ph); ¹³ CNMR (CD₂ Cl₂, 75 MHz, rt) δ176.6 and 174.0 (N═C--C'═N), 162.2 (q, J_(CB)=49.3, BAF: C_(ipso)), 142.8 and142.4 (Ar, Ar': C_(ipso)) 138.2, 137.3,137.1, and 136.9 (Ar, Ar': C_(o)), 135.2 (BAF: C_(o),C_(o) '), 134.6 and132.2 (Ph: C_(o), C_(m), or C_(p))), 129.4 (BAF: C_(m)), 129.0 and 128.5(Ar, Ar': C_(p)), 125.1, 125.1, 124.9 and 124.7 (Ar, Ar': C_(m)), 125.1(q, J_(CF) =272.5, BAF: CF₃), 120.2 (Ph: C_(ipso)) and 120.0 (Ph: C_(o),C_(m), or C_(p)), 117.9 (BAF: C_(p)), 103.0 and 88.6 (Ph: C_(o) ' andC_(m) '), 69.1(CHEtPh), 29.9, 29.7, 29.12 and 29.09 (CHMe₂, C'HMe₂,C"HMe₂, C'"HMe₂), 24.4, 24.3, 23.5, 23.4, 23.1, 23.0, 22.9, and 22.7(CHMeMe', C'HMeMe', C"HMeMe', C"'HMeMe'),20.8, 20.65, and 20.61(N═C(Me)--C'(Me)═N, CH(CH₂ CH₃)Ph)), 13.1 (CH(CH₂ CH₃)Ph).

Example 494 { (2,6-i-PrPh)₂ DABH₂ !Pd(η³ -CHEt(4-C₆ H₄ -t-Bu)!}BAF

t-Butylstyrene (230 μL, 1.26 mmol, 1.10 equiv) was added via microlitersyringe to a mixture of (2,6-i-PrPh)₂ DABH₂ PdMeCl (611 mg, 1.15 mmol)and NaBAF (1.01 g, 1.14 mmol) dissolved in 25 mL of Et₂ O.An additional25 mL of Et₂ O was added to the reaction mixture, which was then stirredfor -12 h. The resulting deep red solution was filtered, and the solventwas removed in vacuo to yield a sticky red solid. The solid was washedwith 150 mL of hexane and the product was dried in vacuo.A dull orangepowder (1.59 g, 91.7%) was obtained: ¹ H NMR (CD₂ Cl₂, 400 MHz, rt)δ8.34 and 8.16 (s, 1 each, N═C(H)--C'(H)═N), 7.72 (s, 8, BAF: H_(o)),7.56 (s, 4, BAF: H_(p)), 7.5-7.1 (m, 8, H_(aryl)), 6.88 (dd, 1, J=7.1,1.9, H_(aryl)), 6.11 (dd, 1, J=7.3, 2.0, H_(aryl)), 3.49, 3.37, 2.64 and2.44 (septet, 1 each, J=6.6-6.9, CHMe₂, C'HMe₂, C"HMe₂ and C'"HMe₂),3.24 (dd, 1, J=11.3, 4.1, CHEt(4-C₆ H₄ -t-Bu)), 1.52, 1.48, 1.24, 1.24,1.19, 1.18, 1.0 and 0.70 (d, 3 each, J=6.8-6.9, CHMeMe', C'HMeMe',C"HMeMe', and C'"HMeMe'), 1.42 and 0.25 (m, 1 each, CH(CHH'CH₃)(4-C₆ H₄-t-Bu)), 0.98 (s, 9, t-Bu), 0.87 (t, 3,J=7.4, CH(CH₂ CH₃) (4-C₆ H₄-t-Bu); ¹³ C NMR (CD₂ Cl₂, 100 MHz, rt) δ165.0 (J_(CH) =165,N═C(H)),163.3 (J_(CH) =165, N═C'(H)), 162.2 (q, J_(CB) =49.9, BAF:C_(ipso)), 157.0 (C₆ H₄ -t-Bu: C_(p)), 144.9 and 144.6 (Ar, Ar':C_(ipso)), 139.0, 138.4, 138.2 and 137.4 (Ar, Ar': C_(o), C_(o) '),135.2 (BAF: C_(o)), 133.3, 129.8, 129.6 and 129.2 (Ar, Ar': C_(p) ; C₆H₄ -t-BU: C_(o), C_(m)), 129.3 (q, BAF: C_(m)), 125.0(q, J_(CF) =272,BAF: CF₃), 124.7, 124.64, 124.55, and 124.3 (Ar, Ar': C_(m), C_(m) '),117.9 (BAF: C_(p)), 119.1, 116.4 and 94.9 (C₆ H₄ -t-Bu: C_(m) ',C_(ipso) ; C_(o) '), 68.5 (CHEt), 36.2 (CMe₃), 30.2 (CMe₃), 30.1, 29.9,28.80 and 28.77 (CHMe₂, C"HMe₂, C"HMe₂ and C'"HMe₂), 25.0, 24.8,24.1,22.8, 22.7, 22.45, 22.36, and 22.1 (CHMeMe', C'HMeMe', C"HMeMe' andC'"HMeMe'), 21.7 (CH(CH₂ CH₃)), 13.2 (CH(CH₂ CH₃)). Anal. Calcd for (C₇₁H₆₇ BF₂₄ N₂ Pd): C, 56.05; H, 4.44; N, 1.84. Found: C, 56.24; H, 4.22;N, 1.59.

Example 495 { (2,6-i-PrPh)₂ DABMe₂ !Pd (η³ -CHEtC₆ F₅)}BAF

A solution of H₂ C═CHC₆ F₅ (138 mg, 0.712 mmol) in 10 mLof Et₂ O wasadded to a mixture of (2,6-i-PrPh)₂ DABMe₂ !PdMeCl (401 mg, 0.713 mmol)and NaBAF (635 mg, 0.716 mmol) dissolved in 25 mL of Et₂ O. After beingstirred for 2 h, the reaction mixture wasfiltered and the solvent wasremoved in vacuo. An orange powder (937 mg, 63.0%) was obtained.

Example 496 { (2,6-i-PrPh)₂ DABH₂ !Ni η³ -CHEt (4-C₆ H₄ -t-Bu)!}BAF

In the drybox, { (2,6-i-PrPh)₂ DABMe₂ !NiMe(OEt₂)}BAF (22.4 mg, 0.0161mmol) was placed in an NMR tube. The tube was sealed with a septum andParafilm®, removed from the drybox, and cooled to -78° C. CD₂ Cl₂ (700μL) and H₂ C═CH(4-C₆ H₄ -t-Bu) (15 μL, 5.10 equiv) were then added viagastight microliter syringe to the cold tube in sequential additions.The septum was sealed with a small amount of grease and more Parafilm,thetube was shaken briefly and then transferred to the cold (-78° C.)NMR probe. Insertion of t-butylstyrene was observed at -78° C. and wascomplete upon warming to -50° C. to yield the π-benzyl complex: ¹ H NMR(CD₂ Cl₂, 400 MHz, -50° C.) δ8.43 and 8.18 (s, 1 each, N═C(H)--C'(H)═N),7.76 (s, 8, BAF: H_(o)), 7.58 (s, 4, BAF: H_(p)), 7.5-7.1 (m, 8,H_(aryl)), 6.80(d, 1, J=7.3, H_(aryl)), 6.15 (d, 1, J=7.7, H_(aryl)),3.72, 3.18, 2.68and 2.50 (septet, 1 each, J=6.5-6.7, CHMe₂, C'HMe₂,C"HMe₂ and C'"HMe₂), 2.56 (dd, 1, J=11.5, 3.9, CHEt), 1.6-0.8 (CHMeMe',C'HMeMe', C"HMeMe', C'"HMeMe', and CH(CHH'CH₃)), 0.94 (s, 9, CMe₃), 0.72(t, 3, J=7.3, CH(CH₂ CH₃)), -0.04 (m, 1, CH(CHH'CH₃)).

Examples 497-515 General Procedure for the Synthesis of π-Allyl TypeNickel Compounds

A mixture of one equiv. of the appropriate α-diimine, one equiv ofNaBAF, and 0.5 equiv of (allyl)Ni(μ-X)!₂ (X═Cl or Br) was dissolved inEt₂ O. The reaction mixture was stirred for ˜2 h before being filtered.The solvent was removes in vacuo to yield the desired product, generallyas a red or purple powder. (The (allyl)Ni(μ-X)!₂ precursors weresynthesized according to the procedures published in the followingreference: Wilke, G.; Bogdanovic, B.; Hardt, P.; Heimbach, P.; Keim, W.;Kroner, M.; Oberkirch, W.; Tanaka, K.; Steinrucke, E.; Walter, D.;Zimmermann, H. Angew. Chem. Int. Ed. Engl.1966, 5, 151-164.) Thefollowing compounds were synthesized according to the above generalprocedure.

Example 497 { (2,4,6-MePh)₂ DABMe₂ !Ni (η³ -C₃ H₅)}BAF Example 498 {(2,6-i-PrPh)₂ DABMe₂ !Ni(η³ -C₃ H₅)}BAF Example 499 { (2,6-i-PrPh)₂DABMe₂ !Ni (η³ -H₂ CCHCHMe)}BAF Example 500 { (2,6-i-PrPh)₂ DABMe₂!Ni(η³ -H₂ CCHCHPh)}BAF Example 501 { (2,6-i-PrPh)₂ DABMe₂ !Ni(η³ -H₂CCHCMe₂)}BAF Example 502 { (2,6-i-PrPh)₂ DABAn!Ni(η³ -C₃ H₅)}BAF Example503 { (2,6-i-PrPh)₂ DABAn!Ni(η³ -H₂ CCHCHMe)}BAF Example 504 {(2,6-i-PrPh)₂ DABAn!Ni(η³ -H₂ CCHCHPh)}BAF Example 505 { (2,6-i-PrPh)₂DABAn!Ni(η³ -H₂ CCHCMe₂)}BAF Example 506 { (2,4,6-MePh)₂ DABAn!Ni(η³ -H₂CCHCHMe)}BAF Example 507 { (2,4,6-MePh)₂ DABAn!Ni(η³ -H₂ CCHCHPh)}BAFExample 508 { (2,4,6-MePh)₂ DABAn!Ni(η³ -C₃ H₅)}BAF Example 509 {(2,4,6-MePh)₂ DABAn!Ni(η³ -H₂ CCHCMe₂)}BAF Example 510 { (2,6-i-PrPh)₂DABAn!Ni(η³ -H₂ CC(COOMe)CH₂)}BAF Example 511 { (2,4,6-MePh)₂DABAn!Ni(η³ -H₂ CC(COOMe)CH₂)}BAF Example 512 { (2,6-i-PrPh)₂DABAn!Ni(η³ -H₂ CCHCH(COOEt)!BAF Example 513 { (2,4,6-MePh)₂ DABAn!Ni(η³-H₂ CCHCH(COOEt)}BAF Example 514 { (2,6-i-PrPh)₂ DABAn!Ni(η³ -H₂CCHCHCl)}BAF Example 515 { (2,4,6-MePh)₂ DABAn!Ni(η³ -H₂ CCHCHCl)}BAFExamples 516-537

Polymerizations catalyzed by nickel and palladium π-benzyl initiatorsand by nickel allyl initiators are illustrated in the following Tablecontaining Examples 516-537. The initiation of polymerizations catalyzedby nickel allyl initiators where the allyl ligand was substituted withfunctional groups, such as chloro or ester groups, was often aided bythe addition of a Lewis acid.

    __________________________________________________________________________    Example         Compound         Conditions   Results    __________________________________________________________________________    516  { (2,6-i-PrPh).sub.2 DABMe.sub.2 !Pd(η.sup.3 -                          0.067 mmol Cmpd; 25° C.; 1                                       <0.5 g PE         CHEtPh)}BAF      atm E; 2 days; CH.sub.2 Cl.sub.2                                       (270 TO)    517  { (2,6-i-PrPh).sub.2 DABMe.sub.2 !Pd(η.sup.3 -                          0.027 mmol Cmpd; 25° C.;                                       8.2 g PE         CHEtPh)}BAF      6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (11,000 TO)    518  { (2,6-i-PrPh).sub.2 DABH.sub.2 !Pd(η.sup.3 -CHEt(4-                          0.016 mmol Cmpd; 25° C.;                                       1.5 g PE         C.sub.6 H.sub.4 -t-Bu))}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (3,300 TO)    519  { 2,6-i-PrPh).sub.2 DABMe.sub.2 !Pd(η.sup.3 -                          0.063 mmol Cmpd; 25° C.; 1                                       4.6 g PE         CHEtC.sub.6 F.sub.5)}BAF                          atm E; 5 days; CH.sub.2 Cl.sub.2                                       (2,600 TO)    520  { (2,6-i-PrPh).sub.2 DABMe.sub.2 !Pd(η.sup.3 -                          0.044 mmol Cmpd; 25°0 C.                                       6.4 g PE         CHEtC.sub.6 F.sub.4)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (5,200 TO)    521  { (2,4,6-MePh).sub.2 DABAn!Ni(η.sup.3 -                          0.049 mmol Cmpd; 25° C.;                                       1.5 g PE         H.sub.2 CCHCMe.sub.2)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (1,100 TO)    522  { (2,4,6-MePh).sub.2 DABMe.sub.2 !Ni(η.sup.3 -                          0.034 mmol Cmpd; 25° C.;                                       35 mg PE         H.sub.2 CCHCMe.sub.2)}BAF                          5.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (37 TO)    523  { (2,4,6-MePh).sub.2 DABMe.sub.2 !Ni(η.sup.3 -                          0.047 mmol Cmpd; 80° C.;                                       20 mg PE         C.sub.5 H.sub.5)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (15 TO)    524  { (2,4,6-MePh).sub.2 DABAn!Ni(η.sup.3 -                          0.034 mmol Cmpd; 80° C.;                                       260 mg PE         C.sub.3 H.sub.5)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (270 TO)    525  { (2,4,6-MePh).sub.2 DABAn!Ni(η.sup.3 -                          0.026 mmol Cmpd; 80° C.;                                       141 mg PE         H.sub.2 CCHCHPh)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (190 TO)    526  { (2,6-i-PrPh).sub.2 DABAn!Ni(η.sup.3 -                          0.040 mmol Cmpd; 80° C.;                                       992 mg PE         H.sub.2 CCHCHPh)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (880 TO)    527  { (2,6-i-PrPh).sub.2 DABAnπNi(η.sup.3 -                          0.043 mmol Cmpd; 80° C.;                                       23 mg PE         H.sub.2 CCHCHMe)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (19 TO)    528  { (2,6-i-PrPh).sub.2 DABMe.sub.2 !Ni(η.sup.3 -                          0.042 mmol Cmpd; 80° C.;                                       15 mg PE         C.sub.3 H.sub.5)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (44 TO)    529  { 2,6-i-PrPh).sub.2 DABAn!Ni(η.sup.3 -                          0.043 mmol Cmpd; 25° C.;                                       15 mg PE         C.sub.3 H.sub.5)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (13 TO)    530  { (2,4,6-MePh).sub.2 DABAn!Ni(η.sup.3 -                          0.043 mmol Cmpd; 25° C.;                                       94 mg PE         H.sub.2 CCHCHCl)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (78 TO)    531  { (2,6-i-PrPh).sub.2 DABAn!Ni(η.sup.3 -                          0.042 mmol Cmpd; 25° C.;                                       8 mg PE         H.sub.2 CCHCHCl)}BAF                          6.9 MPa E; 18 h; C.sub.6 D.sub.6                                       (7 TO)    532  { (2,4,6-MePh).sub.2 DABAn!Ni(η.sup.3 -                          0.020 mmol Cmpd; 0.04                                       7.8 g PE         H.sub.2 CCHCHCl)}BAF                          mmol B(C.sub.6 F.sub.5).sub.3 ; 25° C.;                                       (14,000 TO)                          6.9 MPa E; 18 h; CDCl.sub.3    533  { (2,4,6-MePh).sub.2 DABAn!Ni(η.sup.3 -                          0.020 mmol Cmpd; 0.04                                       8.4 g PE         H.sub.2 CCHCHCl)}BAF                          mmol BPh.sub.3 ; 25° C.;                                       (15,00 TO)                          6.9 MPa E; 18 h; CDCl.sub.3    534  { (2,6-i-PrPh).sub.2 DABAn!Ni(η.sup.3 -                          0.020 mmol Cmpd; 0.04                                       4.7 g PE         H.sub.2 CCHCH(COOEt))}BAF                          mmol BPh.sub.3 ; 25° C.;                                       (8,400 TO)                          6.9 MPa E; 18 h; CDCl.sub.3    535  { 2,6-i-PrPh).sub.2 DABAn!Ni(η.sup.3 -                          0.020 mmol Cmpd; 0.04                                       6.8 g PE         H.sub.2 CCHCHCl)}BAF                          mmol BPh.sub.3 ; 80° C.;                                       (12,000 TO)                          6.9 MPa E; 18 h; C.sub.6 D.sub.6    536  { (2,6-i-PrPh).sub.2 DABAn!Ni(η.sup.3 -                          0.020 mmol Cmpd; 10 mg                                       326 mg PE         H.sub.2 CCHCHCl(}BAF                          montmorillonite; 80° C.; 6.9                                       (580 TO)                          MPa E; 18 h; C.sub.6 D.sub.6    537  { (2,6-i-PrPh).sub.2 DABAn!Ni(η.sup.3 -                          0.020 mmol Cmpd; 0.04                                       10.3 g PE         H.sub.2 CCHCH(COOEt)}BAF                          mmol BPh.sub.3 ; 80° C.;                                       (18,000 TO)                          6.9 MPa E; 18 h; C.sub.6 D.sub.6    __________________________________________________________________________

What is claimed is:
 1. A process for the polymerization of olefins,comprising, contacting a transition metal complex of a bidentate ligandselected from the group consisting of ##STR93## with an olefin wherein:said olefin is selected from the group consisting of ethylene, an olefinof the formula R¹⁷ CH═CH₂ and R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene,norbornene, or a substituted norbornene;said transition metal isselected from the group consisting of Ti, Zr, Sc, V, Cr, a rare earthmetal, Fe, Co, Ni and Pd; R² and R⁵ are each independently hydrocarbylor substituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene or substitutedhydrocarbylene to form a carbocyclic ring; R⁴⁴ is hydrocarbyl orsubstituted hydrocarbyl, and R²⁸ is hydrogen, hydrocarbyl or substitutedhydrocarbyl or R⁴⁴ and R²⁸ taken together form a ring; R⁴⁵ ishydrocarbyl or substituted hydrocarbyl, and R²⁹ is hydrogen, substitutedhydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ taken together form a ring;R⁴⁶ and R⁴⁷ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R⁴⁸ and R⁴⁹ are eachindependently hydrogen, hydrocarbyl, or substituted hydrocarbyl; R³¹ isindependently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R³⁰is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, ortwo of R³⁰ taken together form a ring; R²⁰ and R²³ are independentlyhydrocarbyl or substituted hydrocarbyl; R²¹ and R²² are each inindependently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R¹⁷is independently hydrocarbyl or substituted hydrocarbyl provided thatany olefinic bond in said olefin is separated from any other olefinicbond or aromatic ring by a quaternary carbon atom or at least twosaturated carbon atoms; R¹ is hydrogen, hydrocarbyl or substitutedhydrocarbyl; n is 2 or 3;and provided that: when said bidentate ligandis (XXX) M is not Pd; when M is Pd a diene is not present; and saidtransition metal also has bonded to it a ligand that may be displaced bysaid olefin or add to said olefin; when said olefin comprises norborneneor substituted norbornene no other olefin is present.
 2. The process asrecited in claim 1 wherein said transition metal is Co, Fe, Ni or Pd. 3.The process as recited in claim 1 wherein said transition metal is Ni orPd.
 4. The process as recited in claim 1 wherein said olefin isethylene, R¹⁷ CH═CH₂, or cyclopentene, wherein R¹⁷ is n-alkyl.
 5. Theprocess as recited in claim 1, 2, 3, or 4 wherein said bidentate ligandis (VIII).
 6. The process as recited in claim 5 wherein said olefin isethylene.
 7. The process as recited is in claim 5 wherein said olefin ispropylene.
 8. The process as recited in claim 5 wherein said olefinconsists of of ethylene and propylene.
 9. The process as recited inclaim 5 wherein said olefin is contained in a mixed butenes stream. 10.The process as recited in claim 5 wherein R² and R⁵ are eachindependently hydrocarbyl provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, or R³ and R⁴ takentogether are hydrocarbylene to form a carbocyclic ring.
 11. The processas recited in claim 5 wherein R³ and R₄ are each independently hydrogenor methyl or together are 1,8-naphthylylene, and both R² and R⁵ are2,6-diisopropylphenyl.
 12. The process as recited in claim 5 whereinsaid olefin comprises cyclopentene.
 13. The process as recited in claim1 wherein said olefin comprises cyclopentene.
 14. A process for thecopolymerization of an olefin and a fluorinated olefin, comprising,contacting a transition metal complex of a bidentate ligand selectedfrom the group consisting of ##STR94## with an olefin, and a fluorinatedolefin wherein: said olefin is selected from the group consisting ofethylene and an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷ ;saidtransition metal is selected from the group consisting of Ni and Pd;said fluorinated olefin is of the formula H₂ C═CH (CH₂)_(a) R_(f) R⁴² ;a is an integer of 2 to 20; R_(f) is perfluoroalkylene optionallycontaining one or more ether groups; R⁴² is fluorine or a functionalgroup; R² and R⁵ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R³ andR⁴ taken together are hydrocarbylene or substituted hydrocarbylene toform a carbocyclic ring; each R¹⁷ is independently saturatedhydrocarbyl;and provided that said transition metal also has bonded toit a ligand that may be displaced by said olefin or added to saidolefin.
 15. The process as recited in claim 14 wherein R⁴² is fluorine,ester or sulfonyl halide.
 16. The process as recited in claim 14 or 15wherein said olefin is ethylene or wherein said olefin is R¹⁷ CH═CH₂,wherein R¹⁷ is n-alkyl.
 17. The process as recited in claim 14 whereinR^(f) is --(CF₂)_(b) --, wherein b is 2 to 20, or --(CF₂)_(d) OCF₂ CF₂-- wherein d is 2 to
 20. 18. The process as recited in claim 14 whereinR² and R⁵ are each independently hydrocarbyl, provided that the carbonatom bound to the imino nitrogen atom has at least two carbon atomsbound to it; and R³ and R⁴ are each independently hydrogen, hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene to form a carbocyclicring.
 19. A process for the polymerization of olefins, comprising,contacting, at a temperature of about -100° C. to about +200° C.:a firstcompound W, which is a neutral Lewis acid capable of abstracting eitherQ⁻ and S⁻ to form WQ⁻ or WS⁻, provided that the anion formed is a weaklycoordinating anion; or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion; a second compound of theformula ##STR95## and one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, ornorbornene;wherein: M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co,Ni or Pd in the m oxidation state; y+z=m R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; Q is alkyl, hydride, chloride, iodide,or bromide; S is alkyl, hydride, chloride, iodide, or bromide; andprovided that; when norbornene or substituted norbornene is present, noother monomer is present; when M is Pd a diene is not present; andexcept, when both Q and S are each independently chloride, bromide oriodide w is capable of transferring a hydride or alkyl group to M. 20.The process as recited in claim 19 wherein said monomer is ethyleneonly.
 21. The process as recited in claim 19 wherein said monomer is anα-olefin only.
 22. The process as recited in claim 21 wherein saidα-olefin is propylene.
 23. The process as recited in claim 19 done inthe presence of a solvent.
 24. The process as recited in claim 23wherein R³ and R⁴ are each independently hydrogen or methyl, or R³ andR⁴ taken together are 1,8-naphthylylene, and both R² and R⁵ are2,6-diisopropylphenyl.
 25. The process as recited in claim 19 used tomake a block polymer.
 26. The process as recited in claim 19 wherein:Mis Ti(IV), Q and S are chloride, and y and z are 2; M is Zr(IV), Q and Sare chloride, and y and z are 2; M is Co(II), Q and S are bromide, and yand z are 1; M is Fe(II), Q and S are chloride, and y and z are 1; M isSc(III), Q and S are chloride, y is 1 and z is 2; M is Ni(II), Q and Sare bromide or chloride, and y and z are 1; M is Pd(II), Q and S aremethyl, and y and z are 1; M is Pd(II), Q and S are chloride, and y andz are 1; M is Ni(I), Q is methyl, chloride, bromide, iodide oracetylacetonate, y is 1, and z is 0; M is Pd(II), Q is methyl and S ischloride, and y and z are 1; or M is Ni(II), Q and S are methyl, and yand z are
 1. 27. The process as recited in claim 19 wherein ethylene andpropylene are the monomers.
 28. The process as recited in claim 19wherein said monomers are part of a crude butenes stream.
 29. Theprocess as recited in claim 19 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a carbocyclic ring.
 30. The process as recited inclaim 19 wherein said monomer comprises cyclopentene.
 31. The process asrecited in claim 19 wherein:R² and R⁵ are both 2,4,6-trimethylphenyl or2,6-dimethylphenyl; R³ and R⁴ taken together are 1,8-naphthylylene; yand z are both 1; M is Ni; Q and S are both chloride, iodide or bromide;and m is
 2. 32. The process as recited in claim 31 wherein said firstcompound is an alkylaluminum compound.
 33. The process as recited inclaim 32 wherein said alkylaluminum compound is ethylaluminum dichlorideor methylaluminoxane.
 34. The process as recited in claim 31, 32 or 33wherein said monomer comprises cyclopentene.
 35. The process as recitedin claim 34 wherein cyclopentene is a solvent.
 36. A process for theproduction of polyolefins, comprising, contacting, at a temperature ofabout -100° C. to about +200° C., one or more monomers selected from thegroup consisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene; and a compound of the formula ##STR96## wherein: R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it;R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;T² is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,R¹⁵ C(═O)-- or R¹⁵ OC(═O)--; Z is a neutral Lewis base wherein thedonating atom is nitrogen, sulfur or oxygen, provided that if thedonating atom is nitrogen then the pKa of the conjugate acid of thatcompound is less than about 6; X is a weakly coordinating anion; R¹⁵ ishydrocarbyl not containing olefinic or acetylenic bonds; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms; M is Ni(II) or Pd(II); each R¹⁶ is independently hydrogenor alkyl containing 1 to 10 carbon atoms; n is 1, 2, or 3; R⁸ ishydrocarbyl; and T² is hydrogen, hydrocarbyl not containing olefinic oracetylenic bonds, hydrocarbyl substituted with keto or ester groups butnot containing olefinic or acetylenic bonds, R¹⁵ C(═O)-- or R¹⁵OC(═O)--;provided that: when M is Pd, or (II) or (VII) are present, adiene is not present; and when norbornene or substituted norbornene isused no other monomer is present.
 37. The process as recited in claim 36wherein said monomer is ethylene only.
 38. The process as recited inclaim 36 wherein said monomer is an α-olefin only.
 39. The process asrecited in claim 38 wherein said α-olefin is propylene.
 40. The processas recited in claim 36 wherein said compound is (II), (IV) or (VII), Mis Pd(II), and a comonomer selected from the group consisting of: acompound of the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹, wherein R¹ is hydrogenor, hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbonatoms, and m is 0 or an integer of 1 to 16; CO; and a vinyl ketone, isalso present.
 41. The process as recited in claim 40 wherein m is 0, andR¹ is hydrocarbyl or substituted hydrocarbyl.
 42. The process as recitedin claim 36 done in the presence of a solvent.
 43. The process asrecited in claim 36 done in the absence of a solvent.
 44. The process asrecited in claim 36 wherein R³ and R⁴ are each independently hydrogen ormethyl, or R³ and R⁴ taken together are 1,8-naphthylylene, and both R²and R⁵ are 2,6-diisopropylphenyl.
 45. The process as recited in claim 44wherein X is BAF, SbF₆, PF₆, or BF₄.
 46. The process as recited in claim45 wherein a monomer is ethylene or propylene.
 47. The process asrecited in claim 36 used to make a block polymer.
 48. The process asrecited in claim 36 wherein X is BAF, SbF₆, PF₆, or BF₄.
 49. The processas recited in claim 36 wherein the monomers are ethylene and propylene.50. The process as recited in claim 36 wherein said monomers are part ofa crude butenes stream.
 51. The process as recited in claim 36 whereinR² and R⁵ are each independently hydrocarbyl, provided that the carbonatom bound to the imino nitrogen atom has at least two carbon atomsbound to it; R³ and R⁴ are each independently hydrogen, hydrocarbyl, orR³ and R⁴ taken together are hydrocarbylene to form a carbocyclic ring.52. The process as recited in claim 36 wherein said olefin comprisescyclopentene.
 53. A process for the production of polyolefins,comprising contacting, at a temperature of about -100° C. to about +200°C., one or more monomers selected from the group consisting of ethylene,an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene,cyclopentene, substituted norbornene, and norbornene; with a compound ofthe formula ##STR97## wherein: R²⁰ and R²³ are independently hydrocarbylor substituted hydrocarbyl;R²¹ and R²² are each in independentlyhydrogen, hydrocarbyl or substituted hydrocarbyl; T¹ is hydrogen,hydrocarbyl not containing olefinic or acetylenic bonds, R¹⁵ C(═O)-- orR¹⁵ OC(═O)--; M is Ti, Zr, Sc, Cr, a rare earth metal, V, Fe, Co, Ni orPd in the m oxidation state; for (XIII), m is 2; T² is hydrogen,hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbylsubstituted with keto or ester groups but not containing olefinic oracetylenic bonds, R¹⁵ C(═O)-- or R¹⁵ OC(═O)--; R¹⁵ is hydrocarbyl notcontaining any olefinic or acetyleneic bonds; each R¹⁷ is independentlyhydrocarbyl or substituted hydrocarbyl provided that any olefinic bondin said olefin is separated from any other olefinic bond or aromaticring by a quaternary carbon atom or at least two saturated carbon atoms;Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfuror oxygen, provided that if the donating atom is nitrogen then the pKaof the conjugate acid of that compound is less than about 6; and X is aweakly coordinating anion.
 54. The process as recited in claim 53wherein said monomer is ethylene only.
 55. The process as recited inclaim 54 wherein M is Pd(II) and one or more comonomer is selected fromthe group consisting of: a compound of the formula CH₂ ═CH(CH₂)_(m) CO₂R¹, wherein R¹ is hydrogen or, hydrocarbyl or substituted hydrocarbylcontaining 1 to 10 carbon atoms, and m is 0 or an integer of 1 to 16;CO; and a vinyl ketone is also present.
 56. The process as recited inclaim 55 wherein m is 0, and R¹ is hydrocarbyl or substitutedhydrocarbyl.
 57. The process as recited in claim 53 wherein said monomeris an α-olefin only.
 58. The process as recited in claim 57 wherein saidα-olefin is propylene.
 59. The process as recited in claim 53 done inthe presence of a solvent.
 60. The process as recited in claim 53 donein the absence of a solvent.
 61. The process as recited in claim 53 usedto make a block polymer.
 62. The process as recited in claim 53 whereinX is BAF, SbF₆, PF₆, or BF₄.
 63. The process as recited in claim 62wherein a monomer is ethylene or propylene.
 64. The process as recitedin claim 63 wherein the monomers are ethylene and propylene.
 65. Theprocess as recited in claim 53 wherein said monomers are part of a crudebutenes stream.
 66. The process as recited in claim 53 wherein: orhydrocarbyl; andR²⁰ and R²³ are independently hydrocarbyl.
 67. A processfor the production of polyolefins, comprising contacting, at atemperature of about -100° C. to about +200° C., one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, and norbornene; with a compound of the formula ##STR98## R²¹and R²² are each independently hydrogen, hydrocarbyl or substitutedhydrocarbyl;X is a weakly coordinating anion; R¹⁵ is hydrocarbyl notcontaining any olefinic or acetylenic bonds; each R¹⁷ is independentlyhydrocarbyl or substituted hydrocarbyl provided that any olefinic bondin said olefin is separated from any other olefinic bond or aromaticring by a quaternary carbon atom or at least two saturated carbon atoms;T² is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds,hydrocarbyl substituted with keto or ester groups but not containingolefinic or acetylenic bonds, R¹⁵ C(═O)-- or R¹⁵ OC(═O)--;and providedthat: a diene is not present; and when said olefin comprises norborneneor substituted norbornene no other monomer is present.
 68. The processas recited in claim 67 wherein said monomer is ethylene only.
 69. Theprocess as recited in claim 67 wherein said monomer is an α-olefin only.70. The process as recited in claim 69 wherein said α-olefin ispropylene.
 71. The process as recited in claim 67 wherein T² is methyl;R²⁰ and R²³ are independently hydrocarbyl; and R²¹ and R²² are each inindependently hydrogen or hydrocarbyl.
 72. A process for the productionfor polyolefins, comprising contacting, at a temperature of about -100°C. to about +200° C.,a first compound W, which is a neutral Lewis acidcapable of abstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided thatthe anion formed is a weakly coordinating anion; or a cationic Lewis orBronsted acid whose counterion is a weakly coordinating anion; a secondcompound of the formula ##STR99## and one or more monomers selected fromthe group consisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ orR¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene;wherein: M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe, Sc,or Ni, of oxidation state m; R⁴⁴ is hydrocarbyl or substitutedhydrocarbyl, and R²⁸ is hydrogen, substituted hydrocarbyl orhydrocarbyl, or R⁴⁴ and R²⁸ taken together form a ring; R⁴⁵ ishydrocarbyl or substituted hydrocarbyl, and R²⁹ is hydrogen, substitutedhydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ taken together form a ring;each R³⁰ is independently hydrogen, substituted hydrocarbyl orhydrocarbyl, or two of R³⁰ taken together form a ring; n is 2 or 3; yand z are positive integers; y+z=m; each R¹⁷ is independentlyhydrocarbyl or substituted hydrocarbyl provided that any olefinic bondin said olefin is separated from any other olefinic bond or aromaticring by a quaternary carbon atom or at least two saturated carbon atoms;Q is alkyl, hydride, chloride, iodide, or bromide; S is alkyl, hydride,chloride, iodide, or bromide; and provided that; when norbornene orsubstituted norbornene is present, no other monomer is present.
 73. Theprocess as recited in claim 72 wherein R²⁸, R²⁹, and each of R³⁰ arehydrogen.
 74. The process as recited in claim 72 wherein said monomer isethylene only.
 75. The process as recited in claim 72 wherein saidmonomer is an α-olefin only.
 76. The process as recited in claim 75wherein said α-olefin is propylene.
 77. The process as recited in claim72 done in the presence of a solvent.
 78. The process as recited inclaim 72 wherein both R⁴⁴ and R⁴⁵ are 2,4,6-trimethylphenyl.
 79. Theprocess as recited in claim 78 wherein a monomer is ethylene orpropylene.
 80. The process as recited in claim 72 used to make a blockpolymer.
 81. The process as recited in claim 72 wherein:M is Ti(IV), Qand S are chloride, and y and z are 2; M is Zr(IV), Q and S arechloride, and y and z are 2; M is Co(II), Q and S are bromide, and y andz are 1; M is Fe(II), Q and S are chloride, and y and z are 1; M isSc(III), Q and S are chloride, y is 1 and z is 2; M is Ni(II), Q and Sare bromide or chloride, and y and z are 1; M is Pd(II), Q and S arechloride, and y and z are 1; M is Pd(II), Q and S are methyl, and y andz are 1; M is Ni(I), Q is methyl, chloride, bromide, iodide oracetylacetonate, y is 1, and z is 0; M is Pd(II), Q is methyl and S ischloride, and y and z are 1; or M is Ni(II), Q and S are methyl, and yand z are
 1. 82. The process as recited in claim 72 wherein ethylene andpropylene are the monomers.
 83. The process as recited in claim 72wherein said monomers are part of a crude butenes stream.
 84. Theprocess as recited in claim 72 wherein:R⁴⁴ is hydrocarbyl, and R²⁸ ishydrogen or hydrocarbyl, or R⁴⁴ and R²⁸ taken together form a ring; R⁴⁵is hydrocarbyl, and R²⁹ is hydrogen or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring; and each R³⁰ is independently hydrogen orhydrocarbyl, or two of R³⁰ taken together form a ring.
 85. The processas recited in claim 53 or 72 wherein said compound or said secondcompound is (XVII) and n is 2, all of R³⁰, R²⁸ and R²⁹ are hydrogen, andboth of R⁴⁴ and R⁴⁵ are 9-anthracenyl.
 86. The process as recited inclaim 53 or 72 wherein said compound or said second compound is (XVII)and n is 2, all of R³⁰, R²⁸ and R²⁹ are hydrogen, both of R⁴⁴ and R⁴⁵are 9-anthracenyl, M is Ni.
 87. A process for the production ofpolyolefins, comprising, contacting, at a temperature of about -100° C.to about +200° C., one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene; optionally a source of X⁻, and a compound of the formula##STR100## wherein: R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it;R³ andR⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a carbocyclic ring; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that R¹⁷contains no olefinic bonds; T¹ is hydrogen, hydrocarbyl not containingolefinic or acetylenic bonds, R¹⁵ C(═O)-- or R¹⁵ OC(═O)--; R¹⁵ ishydrocarbyl not containing olefinic or acetylenic bonds; E is halogen or--OR¹⁸ ; R¹⁸ is hydrocarbyl not containing olefinic or acetylenic bonds;and X is a weakly coordinating anion;provided that when norbornene orsubstituted norbornene is present no other monomer is present.
 88. Theprocess as recited in claim 87 wherein said monomer is ethylene only.89. The process as recited in claim 88 wherein E is chlorine and T¹ isalkyl.
 90. The process as recited in claim 89 wherein R³ and R⁴ are eachindependently hydrogen or methyl or R³ and R⁴ taken together are1,8-naphthylylene, both R² and R⁵ are 2,6-diisopropylphenyl, and T¹ ismethyl.
 91. The process as recited in claim 90 wherein X is BAF, SbF₆,PF₆, or BF₄.
 92. The process as recited in claim 91 wherein a monomer isethylene or propylene.
 93. The process as recited in claim 87 whereinsaid monomer is an α-olefin only.
 94. The process as recited in claim 93wherein said α-olefin is propylene.
 95. The process as recited in claim87 wherein E is chlorine.
 96. The process as recited in claim 87 whereinT¹ is alkyl.
 97. The process as recited in claim 87 done in the presenceof a solvent.
 98. The process as recited in claim 87 used to make ablock polymer.
 99. The process as recited in claim 87 wherein themonomers are ethylene and propylene.
 100. The process as recited inclaim 87 wherein said monomers are part of a crude butenes stream. 101.The process as recited in claim 87 wherein R² and R⁵ are eachindependently hydrocarbyl, provided that the carbon atom bound directlyto the imino nitrogen atom has at least two carbon atoms bound to it;and R³ and R⁴ are each independently hydrogen, hydrocarbyl, or R³ and R⁴taken together are hydrocarbylene to form a carbocyclic ring.
 102. Aprocess for the polymerization of olefins, comprising, contacting, at atemperature of about -100° to about +200° C.:a first compound W, whichis a neutral Lewis acid capable of abstracting either Q⁻ or S⁻ to formWQ⁻ or WS⁻, provided that the anion formed is a weakly coordinatinganion; or a cationic Lewis or Bronsted acid whose counterion is a weaklycoordinating anion; a second compound of the formula ##STR101## and oneor more monomers selected from the group consisting of ethylene, anolefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, 4-vinylcyclohexene,cyclobutene, cyclopentene, substituted norbornene, andnorbornene;wherein: M is Ni(II), Co(II), Fe(II) or Pd(II); R² and R⁵ areeach independently hydrocarbyl or substituted hydrocarbyl, provided thatthe carbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;each R¹⁷ is independently hydrocarbyl or substituted hydrocarbylprovided that any olefinic bond in said olefin is separated from anyother olefinic bond or aromatic ring by a quaternary carbon atom or atleast two saturated carbon atoms; Q is alkyl, hydride, chloride, iodide,or bromide; S is alkyl, hydride, chloride, iodide, or bromide;andprovided that: when norbornene or substituted norbornene is present,no other monomer is present, and further provided that when4-vinylcyclohexene is present M is Ni; when M is Pd a diene is notpresent; and when both Q and S are each independently chloride, bromideor iodide W is capable of transferring a hydride or alkyl group to M.103. The process as recited in claim 102 wherein said monomer isethylene only.
 104. The process as recited in claim 102 wherein saidmonomer is an α-olefin only.
 105. The process as recited in claim 104wherein said α-olefin is propylene.
 106. The process as recited in claim102 done in the presence of a solvent.
 107. The process as recited inclaim 102 wherein R³ and R⁴ are each independently hydrogen or methyl orboth of R³ and R⁴ taken together are 1,8-naphthylylene, and both R² andR⁵ are 2,6-diisopropylphenyl.
 108. The process as recited in claim 102used to make a block polymer.
 109. The process as recited in claim 102wherein a monomer is ethylene or propylene.
 110. The process as recitedin claim 102 wherein the molar ratio of said first compound: said secondcompound (I) is about 5 to about
 1000. 111. The process as recited inclaim 110 wherein said first compound is R⁹ AlCl₂, R⁹ ₂ AlCl, R⁹ ₃ Al₂Cl₃, or an alkylaluminoxane in which the alkyl group has 1 to 4 carbonatoms, and wherein R⁹ is alkyl containing 1 to 4 carbon atoms.
 112. Theprocess as recited in claim 102 wherein the molar ratio of said firstcompound: said second compound (I) is about 10 to about
 100. 113. Theprocess as recited in claim 102 wherein said first compound is R⁹ AlCl₂,R⁹ ₂ AlCl, R⁹ ₃ Al₂ Cl₃, or an alkylaluminoxane in which the alkyl grouphas 1 to 4 carbon atoms, and wherein R⁹ is alkyl containing 1 to 4carbon atoms.
 114. The process as recited in claim 102 wherein themonomer comprises cyclopentene.
 115. The process as recited in claim 102wherein said monomers are part of a crude butenes stream.
 116. Theprocess as recited in claim 102 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a carbocyclic ring.
 117. A polymerizationprocess, comprising, contacting a compound of the formula Pd(R¹³ CN)₄!X₂, or a combination of Pd OC(O)R⁴⁰ !₂ and HX, with a compound of theformula ##STR102## and one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene, substituted norbornene, andnorbornene, wherein:R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene or substitutedhydrocarbylene to form a carbocyclic ring; each R¹⁷ is independentlyhydrocarbyl or substituted hydrocarbyl provided R¹⁷ contains no olefinicbonds; R¹³ is hydrocarbyl; R⁴⁰ is hydrocarbyl or substitutedhydrocarbyl; and X is a weakly coordinating anion;provided that whennorbornene or substituted norbornene, is present no other monomer ispresent.
 118. The process as recited in claim 117 wherein said monomeris ethylene only.
 119. The process as recited in claim 117 wherein saidmonomer-is an α-olefin only.
 120. The process as recited in claim 119wherein said α-olefin is propylene.
 121. The process as recited in claim117 wherein one or more comonomer selected from the group consisting of:a compound of the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹, wherein R¹ ishydrogen or, hydrocarbyl or substituted hydrocarbyl containing 1 to 10carbon atoms, and m is 0 or an integer of 1 to 16; CO; and a vinylketone is also present.
 122. The process as recited in claim 121 whereinm is 0, ad R¹ is hydrocarbyl or substituted hydrocarbyl.
 123. Theprocess as recited in claim 117 done in the presence of a solvent. 124.The process as recited in claim 117 wherein R³ and R⁴ are eachindependently hydrogen or methyl or both R³ and R⁴ taken together are1,8-naphthylylene, and both R² and R⁵ are 2,6-diisopropylphenyl. 125.The process as recited in claim 124 wherein X is BAF or BF₄.
 126. Theprocess as recited in claim 125 wherein a monomer is ethylene orpropylene.
 127. The process as recited in claim 117 used to make a blockpolymer.
 128. The process as recited in claim 117 wherein X is BAF,SbF₆, PF₆, or BF₄.
 129. The process as recited in claim 117 wherein themonomers are ethylene and propylene.
 130. The process as recited inclaim 117 wherein said monomers are part of a crude butenes stream. 131.The process as recited in claim 117 wherein R² and R⁵ are eachindependently hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; and R³and R⁴ are each independently hydrogen, hydrocarbyl, or R³ and R⁴ takentogether are hydrocarbylene to form a carbocyclic ring.
 132. Apolymerization process, comprising, contacting:a Ni 0!, Pd 0! or Ni I!compound containing a ligand which may be displaced by a ligand of theformula (VIII), (XXX), (XXXII) or (XXIII); a second compound of theformula ##STR103## an oxidizing agent; a source of a relatively weaklycoordinating anion; and one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene, substituted norbornene, andnorbornene;wherein: R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl orR³ and R⁴ taken together are hydrocarbylene or substitutedhydrocarbylene to form a ring; each R¹⁷ is independently hydrocarbyl orsubstituted hydrocarbyl provided that any olefinic bond in said olefinis separated from any other olefinic bond or aromatic ring by aquaternary carbon atom or at least two saturated carbon atoms; each R³¹is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R⁴⁴is hydrocarbyl or substituted hydrocarbyl, and R²⁸ is hydrogen,hydrocarbyl or substituted hydrocarbyl or R⁴⁴ and R²⁸ taken togetherform a ring; R⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R²⁹ ishydrogen, substituted hydrocarbyl or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring; each R³⁰ is independently hydrogen, substitutedhydrocarbyl or hydrocarbyl, or two of R³ taken together form a ring; R⁴⁶and R⁴⁷ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it; n is 2 or 3; R⁴⁸ and R⁴⁹ are eachindependently hydrogen, hydrocarbyl, or substituted hydrocarbyl; R²⁰ andR²³ are independently hydrocarbyl or substituted hydrocarbyl; R²¹ andR²² are each independently hydrogen, hydrocarbyl or substitutedhydrocarbyl; and provided that; when norbornene or substitutednorbornene is present, no other monomer is present; when a Pd 0!compound is used, a diene is not present; and when said second compoundis (XXX) only an Ni 0! or Ni I! compound is used.
 133. The process asrecited in claim 132 wherein said monomer is ethylene only.
 134. Theprocess as recited in claim 132 wherein said monomer is an α-olefinonly.
 135. The process as recited in claim 134 wherein said α-olefin ispropylene.
 136. The process as recited in claim 132 done in the presenceof a solvent.
 137. The process as recited in claim 132 used to make ablock polymer.
 138. The process as recited in claim 132 wherein themonomers are ethylene and propylene.
 139. The process as recited inclaim 132 wherein said monomers are part of a crude butenes stream. 140.The process as recited in claim 132 wherein:R² and R⁵ are eachindependently hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, or R³ and R⁴ takentogether are hydrocarbylene to form a ring; each R¹⁷ is independentlyhydrocarbyl provided that any olefinic bond in said olefin is separatedfrom any other olefinic bond or aromatic ring by a quaternary carbonatom or at least two saturated carbon atoms; each R⁻ is independentlyhydrogen or hydrocarbyl; R⁴⁴ is hydrocarbyl, and R²⁸ is hydrogen orhydrocarbyl or R⁴⁴ and R²⁸ taken together form a ring; R⁴⁵ ishydrocarbyl, and R²⁹ is hydrogen, or hydrocarbyl, or R⁴⁵ and R²⁹ takentogether form a ring; each R³⁰ is independently hydrogen or hydrocarbyl,or two of R³⁰ taken together form a ring; R⁴⁶ and R⁴⁷ are eachindependently hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R⁴⁸ andR⁴⁹ are each independently hydrogen or hydrocarbyl; R²⁰ and R²³ areindependently hydrocarbyl; and R²¹ and R²² are each in independentlyhydrogen or hydrocarbyl.
 141. The process as recited in claim 132wherein said olefin comprises cyclopentene.
 142. The process as recitedin claim 132 wherein said Ni 0! compound isbis(1,5-cyclooctadiene)nickel or bis(o-tolylphosphito)nickel(ethylene)or said Pd 0! compound is tris(dibenzylideneacetone)dipalladium 0!. 143.The process as recited in claim 1, 3 or 132 wherein said bidentateligand or second compound is (XXX) and n is 2, all of R³⁰, R²⁸ and R²⁹are hydrogen, and both of R⁴⁴ and R⁴⁵ are 9-anthracenyl.
 144. Apolymerization process, comprising, contacting an Ni 0! complexcontaining a ligand or ligands which may be displaced by (VIII), oxygen,an alkyl aluminum compound, and a compound of the formula ##STR104## andone or more monomers selected from the group consisting of ethylene, anolefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene; wherein:R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; and eachR¹⁷ is independently hydrocarbyl or substituted hydrocarbyl providedthat any olefinic bond in said olefin is separated from any otherolefinic bond or aromatic ring by a quaternary carbon atom or at leasttwo saturated carbon atoms;provided that, when norbornene or substitutednorbornene is present, no other monomer is present.
 145. The process asrecited in claim 144 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a carbocyclic ring.
 146. The process as recitedin claim 144 wherein said Ni 0! complex is a 1,5-cyclooctadiene complex.147. The process as recited in claim 144 wherein said monomer isethylene only.
 148. The process as recited in claim 144 wherein saidolefin comprises cyclopentene.
 149. The process as recited in claim 143used to make a block polymer.
 150. The process as recited in claim 144wherein said monomer is an α-olefin only.
 151. The process as recited inclaim 150 wherein said α-olefin is propylene.
 152. The process asrecited in claim 144 done in the presence of a solvent.
 153. The processas recited in claim 144 wherein the monomers are ethylene and propylene.154. The process as recited in claim 144 wherein said monomers are partof a crude butenes stream.
 155. A polymerization process, comprising,contacting oxygen and an alkyl aluminum compound, or a compound of theformula HX, and a compound of the formula ##STR105## and one or moremonomers selected from the group consisting of ethylene, an olefin ofthe formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclopentene, cyclobutene,substituted norbornene, and norbornene; wherein:R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; and eachR¹⁷ is independently hydrocarbyl or substituted hydrocarbyl providedthat any olefinic bond in said olefin is separated from any otherolefinic bond or aromatic ring by a quaternary carbon atom or at leasttwo saturated carbon atoms; X is a weakly coordinating anion;andprovided that, when norbornene or substituted norbornene is present,no other monomer is present.
 156. The process as recited in claim 155wherein R² and R⁵ are each independently hydrocarbyl, provided that thecarbon atom bound to the imino nitrogen atom has at least two carbonatoms bound to it; and R³ and R⁴ are each independently hydrogen,hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form acarbocyclic ring.
 157. The process as recited in claim 156 wherein saidolefin comprises cyclopentene.
 158. The process as recited in claim 156wherein said monomer is ethylene only.
 159. The process as recited inclaim 155 wherein said monomer is ethylene only.
 160. The process asrecited in claim 155 wherein said olefin comprises cyclopentene. 161.The process as recited in claim 155 wherein said monomer is an α-olefinonly.
 162. The process as recited in claim 161 wherein said α-olefin ispropylene.
 163. The process as recited in claim 155 done in the presenceof a solvent.
 164. The process as recited in claim 155 used to make ablock polymer.
 165. The process as recited in claim 155 wherein themonomers are ethylene and propylene.
 166. The process as recited inclaim 155 wherein said monomers are part of a crude butenes stream. 167.A polymerization process, comprising, contacting an Ni 0! complexcontaining a ligand or ligands which may be displaced by (VIII), HX or aBronsted acidic solid, and a compound of the formula ##STR106## an oneor more monomers selected from the group consisting of ethylene, anolefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene; wherein:R² and R⁵are each independently hydrocarbyl or substituted hydrocarbyl, providedthat the carbon atom bound to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms; and X is a weakly coordinating anion; provided that, whennorbornene or substituted norbornene is present, no other monomer ispresent.
 168. The process as recited in claim 167 wherein R² and R⁵ areeach independently hydrocarbyl, provided that the carbon atom bound tothe imino nitrogen atom has at least two carbon atoms bound to it; andR³ and R⁴ are each independently hydrogen, hydrocarbyl, or R³ and R⁴taken together are hydrocarbylene to form a carbocyclic ring.
 169. Theprocess as recited in claim 167 wherein said Ni 0! complex isbis(1,5-cyclooctadiene)nickel or bis(o-tolylphosphito)nickel(ethylene).170. The process as recited in claim 167 wherein said monomer isethylene only.
 171. The process as recited in claim 167 wherein saidolefin comprises cyclopentene.
 172. The process as recited in claim 167wherein said monomer is an α-olefin only.
 173. The process as recited inclaim 172 wherein said α-olefin is propylene.
 174. The process asrecited in claim 167 done in the presence of a solvent.
 175. The processas recited in claim 167 used to make a block polymer.
 176. The processas recited in claim 167 wherein the monomers are ethylene and propylene.177. The process as recited in claim 167 wherein said monomers are partof a crude butenes stream.
 178. A process for the polymerization ofolefins, comprising, contacting, at a temperature of about -100° C. toabout +200° C.:a first compound W, which is a neutral Lewis acid capableof abstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻, provided that theanion formed is a weakly coordinating anion; or a cationic Lewis orBronsted acid whose counterion is a weakly coordinating anion; a secondcompound of the formula ##STR107## and one or more monomers selectedfrom the group consisting of ethylene, an olefin of the formula R¹⁷CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, or norbornene;wherein: M is Ni(II) or Pd(II); R²⁰ and R²³are independently hydrocarbyl or substituted hydrocarbyl; R²¹ and R²²are each in independently hydrogen, hydrocarbyl or substitutedhydrocarbyl; each R¹⁷ is independently hydrocarbyl or substitutedhydrocarbyl provided that any olefinic bond in said olefin is separatedfrom any other olefinic bond or aromatic ring by a quaternary carbonatom or at least two saturated carbon atoms; Q is alkyl, hydride,chloride, iodide, or bromide; S is alkyl, hydride, chloride, iodide, orbromide;provided that; when norbornene or substituted norbornene ispresent, no other monomer is present; when M is Pd a diene is notpresent; and except when M is Pd, when both Q and S are eachindependently chloride, bromide or iodide W is capable of transferring ahydride or alkyl group to M.
 179. The process as recited in claim 178wherein said monomer is ethylene only.
 180. The process as recited inclaim 178 wherein said monomer is an α-olefin only.
 181. The process asrecited in claim 180 wherein said α-olefin is propylene.
 182. Theprocess as recited in claim 178 done in the presence of a solvent. 183.The process as recited in claim 182 wherein a monomer is ethylene orpropylene.
 184. The process as recited in claim 178 used to make a blockpolymer.
 185. The process as recited in claim 178 wherein the molarratio of said first compound: said second compound (I) is about 5 toabout
 1000. 186. The process as recited in claim 178 wherein the molarratio of said first compound: said second compound (I) is about 10 toabout
 100. 187. The process as recited in claim 178 wherein the monomersare ethylene and propylene.
 188. The process as recited in claim 178wherein said monomers are part of a crude butenes stream.
 189. Theprocess as recited in claim 178 wherein R²⁰ and R²³ are independentlyhydrocarbyl; R²¹ and R²² are each in independently hydrogen orhydrocarbyl; and each R¹⁷ is independently hydrocarbyl provided that anyolefinic bond in said olefin is separated from any other olefinic bondor aromatic ring by a quaternary carbon atom or at least two saturatedcarbon atoms.
 190. A process for the polymerization of olefins,comprising, contacting, at a temperature of about -100° C. to about+200° C., a compound of the formula ##STR108## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclopentene, cyclobutene, substitutednorbornene, and norbornene; wherein:R² and R⁵ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound to the imino nitrogen atom has at least two carbon atoms bound toit; R³ and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a carbocyclic ring; each R¹⁷ isindependently hydrocarbyl or substituted hydrocarbyl provided that R¹⁷does not contain any olefinic bonds; and each R²⁷ is independentlyhydrocarbyl; each X is a weakly coordinating anion;provided that, whennorbornene or substituted norbornene is present, no other monomer ispresent.
 191. The process as recited in claim 190 wherein both R²⁷ aremethyl.
 192. The process as recited in claim 190 wherein said monomer isethylene only.
 193. The process as recited in claim 190 wherein saidmonomer is an α-olefin only.
 194. The process as recited in claim 193wherein said α-olefin is propylene.
 195. The process as recited in claim190 wherein one or more comonomer selected from the group consisting of:a compound of the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹, wherein R¹ ishydrogen or, hydrocarbyl or substituted hydrocarbyl containing 1 to 10carbon atoms, and m is 0 or an integer of 1 to 16; CO; and a vinylketone is also present.
 196. The process as recited in claim 195 whereinm is 0, and R¹ is hydrocarbyl or substituted hydrocarbyl.
 197. Theprocess as recited in claim 190 done in the presence of a solvent. 198.The process as recited in claim 190 wherein R³ and R⁴ are eachindependently hydrogen or methyl, and both R² and R⁵ are2,6-diisopropylphenyl.
 199. The process as recited in claim 198 whereinX is BAF or BF₄.
 200. The process as recited in claim 199 wherein amonomer is ethylene or propylene.
 201. The process as recited in claim190 used to make a block polymer.
 202. The process as recited in claim190 wherein X is BAF, SbF₆, PF₆, or BF₄.
 203. The process as recited inclaim 190 wherein the monomers are ethylene and propylene.
 204. Theprocess as recited in claim 190 wherein said monomers are part of acrude butenes stream.
 205. The process as recited in claim 190 whereinR² and R⁵ are each independently hydrocarbyl, provided that the carbonatom bound to the imino nitrogen atom has at least two carbon atomsbound to it; and R³ and R⁴ are each independently hydrogen, hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene to form a carbocyclicring, and each R¹⁷ is hydrocarbyl.
 206. The process as recited in claim190 wherein said olefin comprises cyclopentene.
 207. A process for thepolymerization of olefins, comprising, contacting, at a temperature ofabout -100° C. to about +200° C.:a first compound W, which is a neutralLewis acid capable of abstracting either Q⁻ or S⁻ to form WQ⁻ or WS⁻,provided that the anion formed is a weakly coordinating anion; or acationic Lewis or Bronsted acid whose counterion is a weaklycoordinating anion; a second compound of the formula ##STR109## and oneor more monomers selected from the group consisting of ethylene, anolefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclopentene,cyclobutene, substituted norbornene, and norbornene; wherein: R⁴⁶ andR⁴⁷ are each independently hydrocarbyl or substituted hydrocarbyl,provided that the carbon atom bound to the imino nitrogen atom has atleast two carbon atoms bound to it; R⁴⁸ and R⁴⁹ are each independentlyhydrogen, hydrocarbyl, or substituted hydrocarbyl; each R³¹ isindependently hydrocarbyl, substituted hydrocarbyl, or hydrogen; M isTi, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, Ni, or Pd of oxidationstate m; y and z are positive integers; y+z=m; each R¹⁷ is independentlyhydrocarbyl or substituted hydrocarbyl provided that any olefinic bondin said olefin is separated from any other olefinic bond or aromaticring by a quaternary carbon atom or at least two saturated carbon atoms;Q is alkyl, hydride, chloride, iodide, or bromide; S is alkyl, hydride,chloride, iodide or bromide; andprovided that; when norbornene orsubstituted norbornene is present, no other monomer is present; when Mis Pd a diene is not present; and except when both Q and S are eachindependently chloride, bromide or iodide W is capable of transferring ahydride or alkyl group to M.
 208. The process as recited in claim 207wherein each R¹⁷ is hydrogen.
 209. The process as recited in claim 207wherein said monomer is ethylene only.
 210. The process as recited inclaim 207 wherein said monomer is an α-olefin only.
 211. The process asrecited in claim 210 wherein said α-olefin is propylene.
 212. Theprocess as recited in claim 207 done in the presence of a solvent. 213.The process as recited in claim 207 wherein R⁴⁸ and R⁴⁹ are eachindependently hydrogen or methyl, both R⁴⁶ and R⁴⁷ are2,6-diisopropylphenyl, and T¹ is methyl.
 214. The process as recited inclaim 207 used to make a block polymer.
 215. The process as recited inclaim 207 wherein M is Ni(II).
 216. The process as recited in claim 207wherein M is Pd(II).
 217. The process as recited in claim 216 wherein amonomer is ethylene or propylene.
 218. The process as recited in claim207 wherein:M is Ti(IV), Q and S are chloride, and y and z are 2; M isZr(IV), Q and S are chloride, and y and z are 2; M is Co(II), Q and Sare bromide, and y and z are 1; M is Fe(II), Q and S are chloride, and yand z are 1; M is Sc(III), Q and S are chloride, y is 1 and z is 2; M isNi(II), Q and S are bromide or chloride, and y and z are 1; M is Pd(II),Q and S are methyl, and y and z are 1; M is Ni(I), Q is methyl,chloride, bromide, iodide or acetylacetonate, y is 1, and z is 0;or M isNi(II), Q and S are methyl, and y and z are
 1. 219. The process asrecited in claim 207 wherein the monomers are ethylene and propylene.220. The process as recited in claim 207 wherein said monomers are partof a crude butenes stream.
 221. The process as recited in claim 207wherein:R⁴⁶ and R⁴⁷ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R⁴⁸ and R⁴⁹ are eachindependently hydrogen, hydrocarbyl, or substituted hydrocarbyl; eachR³¹ is independently hydrocarbyl, substituted hydrocarbyl, or hydrogen;and each R¹⁷ is hydrocarbyl.
 222. The process as recited in claim 207wherein said olefin comprises cyclopentene.
 223. A process for theproduction of polyolefins, comprising, contacting, at a temperature ofabout -100° C. to about +200° C., a compound of the formula ##STR110##with one or more monomers selected from the group consisting ofethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷,cyclobutene, cyclopentene, substituted norbornene, andnorbornene,wherein: M is Ni(II) or Pd(II); R² and R⁵ are hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound directly tothe imino nitrogen atom has at least two carbon atoms bound to it; R³and R⁴ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene orsubstituted hydrocarbylene to form a ring; each R¹¹ is independentlyhydrogen, alkyl or --(CH₂)_(m) CO₂ R¹ ; T³ is hydrogen, hydrocarbyl notcontaining olefinic or acetylenic bonds, or --CH₂ CH₂ CH₂ CO₂ R⁸ ; P isa divalent group containing one or more repeat units derived from thepolymerization of one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclopentene, cyclobutene, substituted norbornene, andnorbornene, and, when M is Pd(II), optionally one or more of: a compoundof the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹, CO, or a vinyl ketone; R⁸ ishydrocarbyl; each R¹⁷ is independently hydrocarbyl or substitutedhydrocarbyl provided that any olefinic bond in said olefin is separatedfrom any other olefinic bond or aromatic ring by a quaternary carbonatom or at least two saturated carbon atoms; R¹ is hydrogen, orhydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;m is 0 or an integer of 1 to 16; and X is a weakly coordinatinganion;provided that when norbornene or substituted norbornene is presentno other monomer is present; when M is Pd a diene is not present; andfurther provided that when M is Ni(II) R¹¹ is not --CO₂ R⁸.
 224. Thecompound as recited in claim 223 wherein R² and R⁵ are eachindependently hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; and R³and R⁴ are each independently hydrogen, hydrocarbyl, or R³ and R⁴ takentogether are hydrocarbylene to form a ring; and each R¹⁷ is hydrocarbyl.225. The process as recited in claim 223 wherein T³ is methyl.
 226. Theprocess as recited in claim 225 wherein said monomer is ethylene only,and R¹¹ is hydrogen.
 227. The process as recited in claim 225 whereinsaid monomer is an α-olefin only, and R¹¹ is alkyl.
 228. The process asrecited in claim 227 wherein said α-olefin is propylene, and R¹¹ ismethyl.
 229. The process as recited in claim 225 wherein R³ and R⁴ areeach independently hydrogen or methyl or R³ and R⁴ taken together are1,8-naphthylylene, and both R² and R⁵ are 2,6-diisopropylphenyl. 230.The process as recited in claim 229 wherein X is BAF, SbF₆, PF₆, or BF₄.231. The process as recited in claim 230 wherein a monomer is ethyleneor propylene.
 232. The process as recited in claim 223 wherein M isPd(II), and one or more comonomers selected from the group consistingof: a compound of the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹, wherein R¹ ishydrogen or, hydrocarbyl or substituted hydrocarbyl containing 1 to 10carbon atoms, and m is 0 or an integer of 1 to 16; CO; and a vinylketone is also present.
 233. The process as recited in claim 232 whereinm is 0, and R¹ is hydrocarbyl or substituted hydrocarbyl.
 234. Theprocess as recited in claim 233 wherein m is 0, and R¹ is hydrocarbyl.235. The process as recited in claim 223 done in the presence of asolvent.
 236. The process as recited in claim 223 done in the absence ofa solvent.
 237. The process as recited in claim 223 used to make a blockpolymer.
 238. The process as recited in claim 223 wherein X is BAF,SbF₆, PF₆, or BF₄.
 239. The process as recited in claim 223 wherein themonomers are ethylene and propylene.
 240. The process as recited inclaim 223 wherein said monomers are part of a crude butenes stream. 241.The process as recited in claim 223 wherein said monomers comprisecyclopentene.
 242. A process for the production of polyolefins,comprising, contacting, at a temperature of about -100° C. to about+200° C., a compound of the formula ##STR111## and one or more monomersselected from the group consisting of ethylene, an olefin of the formulaR¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene, substitutednorbornene, and norbornene,wherein: M is Zr, Ti, Sc, V, Cr, a rare earthmetal, Fe, Co, Ni or Pd of oxidation state m; R² and R⁵ are eachindependently hydrocarbyl or substituted hydrocarbyl, provided that thecarbon atom bound directly to the imino nitrogen atom has at least twocarbon atoms bound to it; R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; each R¹¹ isindependently hydrogen or alkyl, or both of R¹¹ taken together arehydrocarbylene to form a carbocyclic ring; T³ is hydrogen, hydrocarbylnot containing olefinic or acetylenic bonds, or --CH₂ CH₂ CH₂ CO₂ R⁸ ; Qis a monoanion; P is a divalent group containing one or more repeatunits derived from the polymerization of one or monomers selected fromthe group consisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ orR¹⁷ CH═CHR¹⁷, cyclopentene, cyclobutene, substituted norbornene, andnorbornene, and, when M is Pd(II), optionally one or more of: a compoundof the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹, CO, or a vinyl ketone; R⁸ ishydrocarbyl; a is 1 or 2; y+a+1=m; each R¹⁷ is independently hydrocarbylor substituted hydrocarbyl provided that any olefinic bond in saidolefin is separated from any other olefinic bond or aromatic ring by aquaternary carbon atom or at least two saturated carbon atoms; R¹ ishydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10carbon atoms; m is 0 or an integer of 1 to 16; and X is a weaklycoordinating anion;provided that, when norbornene or substitutednorbornene is present, no other monomer is present; when M is Pd a dieneis not present; and further provided that, when M is Ni(II), T³ is not--CH₂ CH₂ CH₂ CO₂ R⁸.
 243. The process as recited in claim 242 whereinR² and R⁵ are each independently hydrocarbyl, provided that the carbonatom bound to the imino nitrogen atom has at least two carbon atomsbound to it; and R³ and R⁴ are each independently hydrogen, hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene to form a ring; and eachR¹⁷ is hydrocarbyl.
 244. The process as recited in claim 242 wherein T³is methyl.
 245. The process as recited in claim 244 wherein said monomeris ethylene only, and R¹¹ is hydrogen.
 246. The process as recited inclaim 244 wherein said monomer is an α-olefin only, and R¹¹ is alkyl.247. The process as recited in claim 246 wherein said α-olefin ispropylene, and each R¹¹ is methyl or hydrogen.
 248. The process asrecited in claim 244 wherein R³ and R⁴ are each independently hydrogenor methyl, and both R² and R⁵ are 2,6-diisopropylphenyl.
 249. Theprocess as recited in claim 248 wherein X is BAF, SbF₆, PF₆, or BF₄.250. The process as recited in claim 249 wherein a monomer is ethyleneor propylene.
 251. The process as recited in claim 242 wherein M isPd(II), and one or more comonomer selected from the group consisting of:a compound of the formula CH₂ ═CH(CH₂)_(m) CO₂ R¹, wherein R¹ ishydrogen or, hydrocarbyl or substituted hydrocarbyl containing 1 to 10carbon atoms, and m is 0 or an integer of 1 to 16; CO; and a vinylketone is also present.
 252. The process as recited in claim 251 whereinm is 0, and R¹ is hydrocarbyl or substituted hydrocarbyl.
 253. Theprocess as recited in claim 242 done in the presence of a solvent. 254.The process as recited in claim 242 done in the absence of a solvent.255. The process as recited in claim 244 used to make a block polymer.256. The process as recited in claim 242 wherein X is BAF, SbF₆, PF₆, orBF₄.
 257. The process as recited in claim 242 wherein the monomers areethylene and propylene.
 258. The process as recited in claim 242 whereinsaid monomers are part of a crude butenes stream.
 259. The process asrecited in claim 242 wherein said monomer comprises cyclopentene. 260.The process as recited in claim 242 wherein M is Ni or Pd and m is 2.261. The process as recited in 260 wherein said monomer comprisescyclopentene.
 262. The process as recited in claim 242 wherein M is Ni.263. A polymerization process, comprising, contacting an olefin of theformula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, each R¹⁷ is independently hydrogen,hydrocarbyl, or substituted hydrocarbyl provided that any olefinic bondin said olefin is separated from any other olefinic bond or aromaticring by a quaternary carbon atom or at least two saturated carbon atomswith a catalyst, wherein said catalyst:contains a nickel or palladiumatom in a positive oxidation state; contains a neutral bidentate ligandcoordinated to said nickel or palladium atom, and wherein coordinationto said nickel or palladium atom is through two nitrogen atoms or anitrogen atom and a phosphorus atom; and said neutral bidentate ligand,has an Ethylene Exchange Rate of less than 20,000 L-mol⁻¹ s⁻¹ when saidcatalyst contains a palladium atom, and less than 50,000 L-mol⁻¹ s⁻¹when said catalyst contains a nickel atom; and provided that when M isPd a diene is not present.
 264. The polymerization process as recited inclaim 263 wherein said Ethylene Exchange Rate is less than 10,000L-mol-⁻¹ s⁻¹ when said catalyst contains a palladium atom, and less than25,000 L-mol⁻¹ s⁻¹ when said catalyst contains a nickel atom.
 265. Theprocess as recited in claim 263 wherein said bidentate ligand iscoordinated to said nickel or palladium atom through two nitrogen atoms.266. The process as recited in claim 265 wherein said ligand is anα-diimine.
 267. The process as recited in claim 263 wherein said olefinhas the formula R¹⁷ CH═CH₂, wherein R¹⁷ is hydrogen or n-alkyl.
 268. Aprocess for the polymerization of olefins, comprising, contacting, at atemperature of about -100° C. to about +200° C.:a first compound whichis a source of a relatively noncoordinating monoanion; a second compoundof the formula ##STR112## and one or more monomers selected from thegroup consisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene;wherein: R² and R⁵ are each independently hydrocarbyl orsubstituted hydrocarbyl, provided that the carbon atom bound to theimino nitrogen atom has at least two carbon atoms bound to it; R³ and R⁴are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl,or R³ and R⁴ taken together are hydrocarbylene or substitutedhydrocarbylene to form a ring; each R¹⁷ is independently hydrocarbyl orsubstituted hydrocarbyl provided that R¹⁷ does not contain any olefinicbonds; T¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenicbonds, R¹⁵ C(═O)-- or R¹⁵ OC(═O)--; S is chloride, iodide, or bromide;and provided that, when norbornene or substituted norbornene is present,no other monomer is present.
 269. The process as recited in claim 268used to make a block polymer.
 270. The process as recited in claim 268wherein said monoanion is BAF, SbF₆, PF₆, or BF₄.
 271. The process asrecited in claim 268 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a ring; and each R¹⁷ is saturated hydrocarbyl.272. The process as recited in claim 268 wherein said source is analkali metal salt of said anion.
 273. The process as recited in claim272 wherein said monoanion is BAF⁻, SbF₆ ⁻, PF₆ ⁻, or BF₄ ⁻.
 274. Theprocess as recited in claim 265 wherein T¹ is methyl.
 275. The processas recited in claim 268 wherein said monomer is ethylene only, and R¹¹is hydrogen.
 276. The process as recited in claim 268 wherein one ormore comonomer selected from the group consisting of: a compound of theformula CH₂ ═CH(CH₂)_(m) CO₂ R¹, wherein R¹ is hydrogen or, hydrocarbylor substituted hydrocarbyl containing 1 to 10 carbon atoms, and m is 0or an integer of 1 to 16; CO; and a vinyl ketone is also present. 277.The process as recited in claim 276 wherein a monomer is ethylene orpropylene.
 278. The process as recited in claim 268 done in the presenceof a solvent.
 279. The process as recited in claim 268 wherein themonomers are ethylene and propylene.
 280. A process for the productionof polyolefins, comprising, contacting, at a temperature of about 0° C.to about +200° C., a compound of the formula ##STR113## and one or moremonomers selected from the group consisting of ethylene, an olefin ofthe formula R¹⁷ CH═CH₂ or R¹⁷ CH═CHR¹⁷, cyclobutene, cyclopentene,substituted norbornene, and norbornene,wherein: M is Ni(II) or Pd(II); Ais a π-allyl or π-benzyl group; R² and R⁵ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound directly to the imino nitrogen atom has at least two carbon atomsbound to it; R³ and R⁴ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or R³ and R⁴ taken together are hydrocarbyleneor substituted hydrocarbylene to form a ring; each R¹⁷ is independentlyhydrocarbyl or substituted hydrocarbyl provided that any olefinic bondin said olefin is separated from any other olefinic bond or aromaticring by a quaternary carbon atom or at least two saturated carbon atoms;R¹ is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1to 10 carbon atoms; and X is a weakly coordinating anion;and providedthat; when norbornene or substituted norbornene is present, no othermonomer is present; and when M is Pd a diene is not present.
 281. Theprocess as recited in claim 280 wherein said temperature is about 20° C.to about 100° C.
 282. The process as recited in claim 280 wherein saidolefin is ethylene or a linear α-olefin.
 283. The process as recited inclaim 280 or 282 wherein a Lewis acid is also present.
 284. The processas recited in claim 280 wherein said olefin is ethylene.
 285. Theprocess as recited in claim 280 wherein R² and R⁵ are each independentlyhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; and R³ and R⁴ are eachindependently hydrogen, hydrocarbyl, or R³ and R⁴ taken together arehydrocarbylene to form a ring.
 286. The process as recited in claim 280wherein M is Ni(II).
 287. The process as recited in claim 280 wherein Mis Pd(II).
 288. The process as recited in claim 280 wherein said π-allylor π-benzyl group is selected from the group consisting of ##STR114##wherein R is hydrocarbyl.
 289. The process as recited in claim 280wherein said olefin comprises cyclopentene.
 290. A process for thepolymerization of olefins, comprising, contacting a compound of theformula ##STR115## and one or more monomers selected from the groupconsisting of ethylene, an olefin of the formula R¹⁷ CH═CH₂ or R¹⁷CH═CHR¹⁷, cyclobutene, cyclopentene, substituted norbornene, andnorbornene,wherein: R³ and R⁴ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or R³ and R⁴ taken together arehydrocarbylene or substituted hydrocarbylene to form a ring; R⁵⁴ ishydrocarbyl or substituted hydrocarbyl, provided that the carbon atombound directly to the imino nitrogen atom has at least two carbon atomsbound to it; each R⁵⁵ is independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or a functional group; M is Ni or Pd; W isalkylene or substituted alkylene containing 2 or more carbon atoms; Z isa neutral Lewis base wherein the donating atom is nitrogen, sulfur, oroxygen, provided that if the donating atom is nitrogen then the pKa ofthe conjugate acid of that compound (measured in water) is less thanabout 6, or an olefin of the formula R¹⁷ CH═CHR¹⁷ ; each R¹⁷ isindependently hydrogen, saturated hydrocarbyl or substituted saturatedhydrocarbyl; and X is a weakly coordinating anion;and provided that:when M is Ni, W is alkylene and each R¹⁷ is independently hydrogen orsaturated hydrocarbyl;and when norbornene or substituted norbornene ispresent, no other monomer is present.
 291. The process as recited inclaim 290 wherein R³ and R⁴ are each independently hydrogen orhydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene to form aring; and R⁵⁴ is hydrocarbyl.
 292. The process as recited in claim 290or 291 wherein each R⁵⁵ is independently hydrogen or alkyl containing 1to 10 carbon atoms.
 293. The process as recited in claim 290 wherein Zis a dialkyl ether.
 294. The process as recited in claim 290 wherein Zis R¹⁷ CH═CHR¹⁷.
 295. The process as recited in claim 294 wherein saidolefin is ethylene, propylene or a combination of ethylene andpropylene.
 296. The process as recited in claim 290 wherein each R¹⁷ isindependently saturated hydrocarbyl or hydrogen.
 297. The process asrecited in claim 290 wherein both of R¹⁷ are hydrogen.
 298. The processas recited in claim 290 wherein W is --CH(CH₃)CH₂ -- or --C(CH₃)₂ CH₂--.
 299. The process as recited in claim 295 wherein said olefin iscyclopentene.
 300. The process as recited in claim 290 wherein saidtemperature is about 20° C. to about 100° C.
 301. The process as recitedin claim 290 wherein said olefin is ethylene or a linear α-olefin. 302.The process as recited in claim 290 wherein said olefin is ethylene,propylene or a combination of ethylene and propylene.
 303. The processas recited in claim 290 wherein said olefin is cyclopentene.
 304. Theprocess as recited in claim 36, 87, 167, 190, 223, 242, 280 or 290wherein X is part of a heterogeneous support.
 305. The process asrecited in claim 36, 87, 167, 190, 223, 242, 280 or 290 wherein apolymerization catalyst is supported on a heterogeneous support. 306.The process as recited in claim 36, 87, 167, 190, 223, 242, 280 or 290wherein the polymerization is run in the gas phase.
 307. The process asrecited in claim 306 which is run in a fluidized bed reactor.
 308. Theprocess as recited in claim 53 wherein said olefin comprisescyclopentene.
 309. The process as recited in claim 13, 30, 114, 141,148, 160, 171, 222, 241, 259, 52, 308, 289 or 261 wherein cyclopenteneis a solvent.